Phosphinyl formamidine compounds, metal complexes, catalyst systems, and their use to oligomerize or polymerize olefins

ABSTRACT

N 2 -phosphinyl formamidine compounds and N 2 -phosphinyl formamidine metal salt complexes are described. Methods for making N 2 -phosphinyl formamidine compounds and N 2 -phosphinyl formamidine metal salt complexes are also disclosed. Catalyst systems utilizing the N 2 -phosphinyl formamidine metal salt complexes are also disclosed along with the use of the N 2 -phosphinyl amidine compounds and N 2 -phosphinyl amidinate metal salt complexes for the oligomerization and/or polymerization of olefins.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a filing under 35 U.S.C. 371 of InternationalApplication No. PCT/US2013/075936 filed Dec. 18, 2013, entitled“Phosphinyl Formamidine Compounds, Metal Complexes, Catalyst Systems,and Their Use to Oligomerize or Polymerize Olefins,” which applicationis incorporated by reference herein in its entirety.

TECHNICAL FIELD

This disclosure relates to N²-phosphinyl formamidine compounds, metalcomplexes of N²-phosphinyl formamidine compounds and their production.The disclosure also relates to methods of producing the N²-phosphinylformamidine compounds and the metal complexes of N²-phosphinylformamidine compounds. The disclosure further relates to catalystsystems utilizing the N²-phosphinyl formamidine compounds, metalcomplexes of N²-phosphinyl formamidine compounds, and their use in theoligomerization or polymerization of olefins.

BACKGROUND

Olefins, also commonly known as alkenes, are important items ofcommerce. Their many applications include employment as intermediates inthe manufacture of detergents, as precursors to more environmentallyfriendly refined oils, as monomers, and as precursors for many othertypes of products. An important subset of olefins are olefin oligomers,and one method of making olefin oligomers is via oligomerization ofethylene, which is a catalytic reaction involving various types ofcatalysts and/or catalyst systems. Examples of catalysts and catalystsystems used commercially in the oligomerization of olefins includealkylaluminum compounds, certain nickel-phosphine complexes, a titaniumhalide with a Lewis acid (e.g., diethyl aluminum chloride), and aselective 1-hexene catalyst system containing a chromium containingcompound (e.g., a chromium carboxylate), a nitrogen containing ligand(e.g., a pyrrole), and a metal alkyl (e.g., alkyl aluminum compounds).

Several non-commercial olefin oligomerization catalyst systems are basedupon metal complexes of pyridine bis-imines, metal complexes ofα-diimine compounds having a metal complexing group, and selectivetrimerization and/or tetramerization catalyst system using a metalcomplex of a compound having a diphosphinylaminyl group. These catalystsystems typically use an alkyl aluminum compound (e.g., aluminoxane) toactivate the metal complexes for olefin oligomerization.

Applications and demand for olefin oligomers (e.g., alpha olefins)continue to multiply, and competition to supply them correspondinglyintensifies. Thus, additional novel and improved catalysts and methodsfor olefin oligomerization are desirable.

SUMMARY

In an aspect, the present disclosure relates to a compound comprising anN²-phosphinyl formamidine group. In an aspect, the present disclosurerelates to a metal complex comprising a metal salt complexed to acompound having an N²-phosphinyl formamidine group. In an embodiment,the metal salt complex can comprise a Group 4-10 metal salt complexed toa compound comprising an N²-phosphinyl formamidine group. In anembodiment, the metal salt complex can comprise chromium. In anembodiment, the metal salt of the metal salt complex can be a chromiumhalide or chromium β-diketonate.

In an aspect, the present disclosure relates to a method of preparing acompound comprising an N²-phosphinyl formamidine group. In anembodiment, the method for preparing a compound comprising anN²-phosphinyl formamidine group can comprise: a) contacting an aminehaving the formula R¹NH₂ and a trihydrocarbylformate to form aformamidine compound; b) contacting a metal alkyl with the formamidinecompound to form a metal formamidinate; and c) contacting a phosphinehalide with the metal formamidinate to form a compound comprising theN²-phosphinyl formamidine group. In some embodiments, the method forpreparing an N²-phosphinyl formamidine compound can comprise: a)contacting an amine having the formula R¹NH₂ and a trihydrocarbylformateto form a hydrocarboxymethanimine compound; b) contacting an ammoniumcarbonate with the hydrocarboxymethanimine to form a formamidinecompound; c) contacting a metal alkyl with the formamidine compound toform a metal formamidinate; and d) contacting a phosphine halide withthe metal formamidinate to form a compound comprising the N²-phosphinylformamidine group.

In an aspect, the present disclosure relates to a method of preparing anN²-phosphinyl formamidine metal salt complex. In an embodiment, themethod of preparing the N²-phosphinyl formamidine metal salt complex cancomprise: a) contacting a metal salt with an N²-phosphinyl formamidinecompound; and b) forming the N²-phosphinyl formamidine metal saltcomplex.

In an aspect, the present disclosure relates to a catalyst systemcomprising a metal salt complexed to a compound having an N²-phosphinylformamidine group and a metal alkyl. In another aspect, the presentdisclosure relates to a catalyst system comprising a metal salt, acompound having an N²-phosphinyl formamidine group, and a metal alkyl.In an embodiment, the metal salt of the metal salt complex or thecatalyst system can comprise a Group 4-10 metal salt. In someembodiments, the metal salt of the metal salt complex or the catalystsystem can comprise chromium. In other embodiments, the metal salt ofthe metal salt complex or the catalyst system can comprise a chromiumhalide or chromium β-diketonate.

In an aspect, the present disclosure relates to an oligomerizationprocess or a polymerization process. In an embodiment, a process cancomprise: contacting an olefin, a catalyst system comprising i) anN²-phosphinyl formamidine metal salt complex and ii) a metal alkyl, andoptionally hydrogen; and b) forming an oligomer product (or polymerproduct). In an embodiment, a process can comprise: contacting anolefin, a catalyst system comprising i) an N²-phosphinyl formamidinecompound, ii) a metal salt, and iii) a metal alkyl, and optionallyhydrogen; and b) forming an oligomer product (or polymer product). Insome embodiments, a process can comprise: a) forming a catalyst systemmixture comprising an N²-phosphinyl formamidine metal salt complex, anda metal alkyl; b) contacting the catalyst system mixture with an olefin,and optionally hydrogen; and c) forming an oligomer product (or polymerproduct). In other embodiments, a process can comprise: a) forming acatalyst system mixture comprising an N²-phosphinyl formamidine metalsalt complex, a metal alkyl, and a first solvent; b) contacting thecatalyst system mixture with an olefin, a second solvent, and optionallyhydrogen; and c) forming an oligomer product (or polymer product). Inyet another embodiment, a process can comprise: a) forming a catalystsystem mixture comprising an N²-phosphinyl formamidine compound, a metalsalt, and a metal alkyl; b) contacting the catalyst system mixture ofstep a) with an olefin and optionally hydrogen; and c) forming anoligomer product. In yet another embodiment, a process can comprise: a)forming a catalyst system mixture comprising an N²-phosphinylformamidine compound, a metal salt, a metal alkyl, and a first solvent;b) contacting the catalyst system mixture with an olefin, a secondsolvent, and optionally hydrogen; and c) forming an oligomer product.

In an embodiment, the metal salt or the metal salt of the N²-phosphinylformamidine metal salt complex can comprise a Group 4-10 metal salt; oralternatively, a chromium salt. In some embodiments, the metal salt orthe metal salt of the N²-phosphinyl formamidine metal salt complex cancomprise a chromium halide or chromium β-diketonate. In an embodiment,the olefin utilized in oligomerization or polymerization process cancomprise, or consist essentially of, C₂ to C₃₀ olefin; alternatively, aC₂ to C₃₀ alpha olefin; alternatively, a C₂ to C₃₀ normal alpha olefin;alternatively, ethylene or propylene; or alternatively, ethylene. In anembodiment wherein the olefin is ethylene, the oligomerization processcan be an ethylene trimerization process and/or an ethylenetetramerization process. In some embodiments, the ethylene trimerizationprocess and/or ethylene tetramerization process can produce an oligomerproduct comprising a liquid product comprising at least 60 wt. % C₆ andC₈ olefins.

Disclosed herein is an N²-phosphinyl formamidine compound having theformula:

-   -   wherein R¹ is a C₁ to C₃₀ organyl group, R³ is hydrogen, a C₁ to        C₃₀ organyl group, or a C₁ to C₃₀ organyl group consisting        essentially of inert functional groups, and R⁴ and R⁵ are each        independently a C₁ to C₃₀ organyl group consisting essentially        of inert functional groups.

Also disclosed herein is a method of preparing an N²-phosphinylformamidine compound, comprising a) contacting a metal alkyl with aformamidine compound to form a metal formamidinate; and b) contacting aphosphine halide with the metal formamidinate to form a compoundcomprising an N²-phosphinyl formamidine group.

Also disclosed herein is a metal salt complex of an N²-phosphinylformamidine compound having the formula

-   -   or the formula

-   -   wherein R¹ is a C₁ to C₃₀ organyl group, R³ is hydrogen, a C₁ to        C₃₀ organyl group, or a C₁ to C₃₀ organyl group consisting        essentially of inert functional groups, R⁴ and R⁵ are each        independently a C₁ to C₃₀ organyl group consisting essentially        of inert functional groups, MX_(p) represents the metal salt        where M is a transition metal, X is a monoanion and p ranges        from 2 to 6, or X is a dianion and p ranges from 1 to 3, Q is a        neutral ligand, and q ranges from 0 to 6.

Also disclosed herein is a method of preparing an N²-phosphinylformamidine metal salt complex having the formula

-   -   comprising a) contacting a transition metal salt with an        N²-phosphinyl formamidine compound; and b) forming the        N²-phosphinyl formamidine metal salt complex.

Also disclosed herein is a catalyst system comprising a) anN²-phosphinyl formamidine metal salt complex having the formula

-   -   or the formula

-   -   wherein R¹ is a C₁ to C₃₀ organyl group, R³ is hydrogen, a C₁ to        C₃₀ organyl group, or a C₁ to C₃₀ organyl group consisting        essentially of inert functional groups, R⁴ and R⁵ are each        independently a C₁ to C₃₀ organyl group consisting essentially        of inert functional groups, MX_(p) represents the metal salt        where M is a transition metal, X is a monoanion and p ranges        from 2 to 6, or X is a dianion and p ranges from 1 to 3, Q is a        neutral ligand, and q ranges from 0 to 6 and b) a metal alkyl.

Also disclosed herein is a process comprising a) contacting an olefinand a catalyst comprising a) an N²-phosphinyl formamidine metal saltcomplex having the formula

-   -   or the formula

-   -   wherein R¹ is a C₁ to C₃₀ organyl group, R³ is hydrogen, a C₁ to        C₃₀ organyl group, or a C₁ to C₃₀ organyl group consisting        essentially of inert functional groups, R⁴ and R⁵ are each        independently a C₁ to C₃₀ organyl group consisting essentially        of inert functional groups, MX_(p) represents the metal salt        where M is a transition metal, X is a monoanion and p ranges        from 2 to 6, or X is a dianion and p ranges from 1 to 3, Q is a        neutral ligand, and q ranges from 0 to 6 and b) a metal alkyl        wherein the metal alkyl is an aluminoxane; and b) forming an        oligomer product. The method disclosed herein further comprises        contacting the catalyst system mixture with an olefin and        forming an oligomer product.

DETAILED DESCRIPTION Definitions

To define more clearly the terms used herein, the following definitionsare provided. Unless otherwise indicated, the following definitions areapplicable to this disclosure. If a term is used in this disclosure butis not specifically defined herein, the definition from the IUPACCompendium of Chemical Terminology, 2^(nd) Ed (1997) can be applied, aslong as that definition does not conflict with any other disclosure ordefinition applied herein, or render indefinite or non-enabled any claimto which that definition is applied. To the extent that any definitionor usage provided by any document incorporated herein by referenceconflicts with the definition or usage provided herein, the definitionor usage provided herein controls.

Groups of elements of the table are indicated using the numbering schemeindicated in the version of the periodic table of elements published inChemical and Engineering News, 63(5), 27, 1985. In some instances agroup of elements can be indicated using a common name assigned to thegroup; for example alkali earth metals (or alkali metals) for Group 1elements, alkaline earth metals (or alkaline metals) for Group 2elements, transition metals for Group 3-12 elements, and halogens forGroup 17 elements.

Regarding claim transitional terms or phrases, the transitional term“comprising”, which is synonymous with “including,” “containing,”“having,” or “characterized by,” is inclusive or open-ended and does notexclude additional, unrecited elements or method steps. The transitionalphrase “consisting of” excludes any element, step, or ingredient notspecified in the claim. The transitional phrase “consisting essentiallyof” limits the scope of a claim to the specified materials or steps andthose that do not materially affect the basic and novelcharacteristic(s) of the claimed invention. A “consisting essentiallyof” claim occupies a middle ground between closed claims that arewritten in a “consisting of” format and fully open claims that aredrafted in a “comprising” format. Absent an indication to the contrary,when describing a compound or composition “consisting essentially of” isnot to be construed as “comprising,” but is intended to describe therecited component that includes materials which do not significantlyalter the composition or method to which the term is applied. Forexample, a feedstock consisting of a material A can include impuritiestypically present in a commercially produced or commercially availablesample of the recited compound or composition. When a claim includesdifferent features and/or feature classes (for example, a method step,feedstock features, and/or product features, among other possibilities),the transitional terms comprising, consisting essentially of, andconsisting of apply only to the feature class which is utilized and itis possible to have different transitional terms or phrases utilizedwith different features within a claim. For example, a method cancomprise several recited steps (and other non-recited steps) but utilizea catalyst system preparation consisting essentially of specific oralternatively consists of specific steps and/or utilize a catalystsystem comprising recited components and other non-recited components.

While compositions and methods are described in terms of “comprising”various components or steps, the compositions and methods can also“consist essentially of” or “consist of” the various components orsteps.

The terms “a,” “an,” and “the” are intended, unless specificallyindicated otherwise, to include plural alternatives, e.g., at least one.For instance, the disclosure of “a trialkylaluminum compound” is meantto encompass one trialkylaluminum compound, or mixtures or combinationsof more than one trialkylaluminum compound unless otherwise specified.

For any particular compound disclosed herein, the general structure orname presented is also intended to encompass all structural isomers,conformational isomers, and stereoisomers that can arise from aparticular set of substituents, unless indicated otherwise. Thus, ageneral reference to a compound includes all structural isomers unlessexplicitly indicated otherwise; e.g., a general reference to pentaneincludes n-pentane, 2-methyl-butane, and 2,2-dimethylpropane while ageneral reference to a butyl group includes an n-butyl group, asec-butyl group, an iso-butyl group, and a tert-butyl group.Additionally, the reference to a general structure or name encompassesall enantiomers, diastereomers, and other optical isomers whether inenantiomeric or racemic forms, as well as mixtures of stereoisomers, asthe context permits or requires. For any particular formula or name thatis presented, any general formula or name presented also encompasses allconformational isomers, regioisomers, and stereoisomers that can arisefrom a particular set of substituents.

A chemical “group” is described according to how that group is formallyderived from a reference or “parent” compound, for example, by thenumber of hydrogen atoms formally removed from the parent compound togenerate the group, even if that group is not literally synthesized inthis manner. These groups can be utilized as substituents or coordinatedor bonded to metal atoms. By way of example, an “alkyl group” formallycan be derived by removing one hydrogen atom from an alkane, while an“alkylene group” formally can be derived by removing two hydrogen atomsfrom an alkane. Moreover, a more general term can be used to encompass avariety of groups that formally are derived by removing any number (“oneor more”) hydrogen atoms from a parent compound, which in this examplecan be described as an “alkane group,” and which encompasses an “alkylgroup,” an “alkylene group,” and materials have three or more hydrogensatoms, as necessary for the situation, removed from the alkane.Throughout the disclosure a substituent, ligand, or other chemicalmoiety can constitute a particular “group” implies that the well-knownrules of chemical structure and bonding are followed when that group isemployed as described. When describing a group as being “derived by,”“derived from,” “formed by,” or “formed from,” such terms are used in aformal sense and are not intended to reflect any specific syntheticmethods or procedure, unless specified otherwise or the context requiresotherwise.

The term “substituted” when used to describe a group, for example, whenreferring to a substituted analog of a particular group, is intended todescribe any non-hydrogen moiety that formally replaces a hydrogen inthat group, and is intended to be non-limiting. A group or groups canalso be referred to herein as “unsubstituted” or by equivalent termssuch as “non-substituted,” which refers to the original group in which anon-hydrogen moiety does not replace a hydrogen within that group.“Substituted” is intended to be non-limiting and include inorganicsubstituents or organic substituents.

A formamidine group is a group having the general structure

Within the formamidine group the nitrogen participating in a double bondwith the central carbon atom is referred to as the N¹ nitrogen and thenitrogen atom participating in a single bond with the central carbonatom is referred to as the N² nitrogen. Similarly, the groups attachedto the N¹ and N² nitrogen atoms are referred to as the N¹ group and N²group respectively. An N²-phosphinyl formamidine group has the generalstructure

Within the N²-phosphinyl formamidine group the N¹ and N² nitrogen atomsand N¹ and N² groups have the same meaning as described for theformamidine group. Consequently, an N²-phosphinyl formamidine group hasthe phosphinyl group is attached to the N² nitrogen atom.

The term “organyl group” is used herein in accordance with thedefinition specified by IUPAC: an organic substituent group, regardlessof functional type, having one free valence at a carbon atom. Similarly,an “organylene group” refers to an organic group, regardless offunctional type, derived by removing two hydrogen atoms from an organiccompound, either two hydrogen atoms from one carbon atom or one hydrogenatom from each of two different carbon atoms. An “organic group” refersto a generalized group formed by removing one or more hydrogen atomsfrom carbon atoms of an organic compound. Thus, an “organyl group,” an“organylene group,” and an “organic group” can contain organicfunctional group(s) and/or atom(s) other than carbon and hydrogen, thatis, an organic group can comprise functional groups and/or atoms inaddition to carbon and hydrogen. For instance, non-limiting examples ofatoms other than carbon and hydrogen include halogens, oxygen, nitrogen,phosphorus, and the like. Non-limiting examples of functional groupsinclude ethers, aldehydes, ketones, esters, sulfides, amines,phosphines, and so forth. In one aspect, the hydrogen atom(s) removed toform the “organyl group,” “organylene group,” or “organic group” can beattached to a carbon atom belonging to a functional group, for example,an acyl group (—C(O)R), a formyl group (—C(O)H), a carboxy group(—C(O)OH), a hydrocarboxycarbonyl group (—C(O)OR), a cyano group (—C≡N),a carbamoyl group (—C(O)NH₂), a N-hydrocarbylcarbamoyl group (—C(O)NHR),or N,N′-dihydrocarbylcarbamoyl group (—C(O)NR₂), among otherpossibilities. In another aspect, the hydrogen atom(s) removed to formthe “organyl group,” “organylene group,” or “organic group” can beattached to a carbon atom not belonging to, and remote from, afunctional group, for example, —CH₂C(O)CH₃, —CH₂NR₂, and the like. An“organyl group,” “organylene group,” or “organic group” can bealiphatic, inclusive of being cyclic or acyclic, or can be aromatic.“Organyl groups,” “organylene groups,” and “organic groups” alsoencompass heteroatom-containing rings, heteroatom-containing ringsystems, heteroaromatic rings, and heteroaromatic ring systems. “Organylgroups,” “organylene groups,” and “organic groups” can be linear orbranched unless otherwise specified. Finally, it is noted that the“organyl group,” “organylene group,” or “organic group” definitionsinclude “hydrocarbyl group,” “hydrocarbylene group,” “hydrocarbongroup,” respectively, and “alkyl group,” “alkylene group,” and “alkanegroup,” respectively, as members.

For the purposes of this application, the term or variations of the term“organyl group consisting of inert functional groups” refers to anorganyl group wherein the organic functional group(s) and/or atom(s)other than carbon and hydrogen present in the functional group arerestricted to those functional group(s) and/or atom(s) other than carbonand hydrogen which do not complex with a metal compound and/or are inertunder the process conditions defined herein. Thus, the term or variationof the term “organyl group consisting of inert functional groups”further defines the particular organyl groups that can be present withinthe organyl group consisting of inert functional groups. Additionally,the term “organyl group consisting of inert functional groups” can referto the presence of one or more inert functional groups within theorganyl group. The term or variation of the term “organyl groupconsisting of inert functional groups” definition includes thehydrocarbyl group as a member (among other groups). Similarly, an“organylene group consisting of inert functional groups” refers to anorganic group formed by removing two hydrogen atoms from one or twocarbon atoms of an organic compound consisting of inert functionalgroups and an “organic group consisting of inert functional groups”refers to a generalized organic group consisting of inert functionalgroups formed by removing one or more hydrogen atoms from one or morecarbon atoms of an organic compound consisting of inert functionalgroups.

For purposes of this application, an “inert functional group” is a groupwhich does not substantially interfere with the process described hereinin which the material having an inert functional group takes part and/ordoes not complex with the metal compound of the metal complex. The term“does not complex with the metal compound” can include groups that couldcomplex with a metal compound but in particular molecules describedherein may not complex with a metal compound due to its positionalrelationship within a ligand. For example, while an ether group cancomplex with a metal compound, an ether group located at a para positionof a substituted phenyl phosphinyl group may be an inert functionalgroup because a single metal compound cannot complex with both the paraether group and the N²-phosphinyl formamidine group of the same metalcomplex molecule. Thus, the inertness of a particular functional groupis not only related to the functional group's inherent inability tocomplex the metal compound but can also be related to the functionalgroup's position within the metal complex. Non-limiting examples ofinert functional groups which do not substantially interfere withprocesses described herein can include halo (fluoro, chloro, bromo, andiodo), nitro, hydrocarboxy groups (e.g., alkoxy, and/or aroxy, amongothers), sulfidyl groups, and/or hydrocarbyl groups, among others.

The term “hydrocarbon” whenever used in this specification and claimsrefers to a compound containing only carbon and hydrogen. Otheridentifiers can be utilized to indicate the presence of particulargroups in the hydrocarbon (e.g. halogenated hydrocarbon indicates thatthe presence of one or more halogen atoms replacing an equivalent numberof hydrogen atoms in the hydrocarbon). The term “hydrocarbyl group” isused herein in accordance with the definition specified by IUPAC: aunivalent group formed by removing a hydrogen atom from a hydrocarbon.Non-limiting examples of hydrocarbyl groups include ethyl, phenyl,tolyl, propenyl, and the like. Similarly, a “hydrocarbylene group”refers to a group formed by removing two hydrogen atoms from ahydrocarbon, either two hydrogen atoms from one carbon atom or onehydrogen atom from each of two different carbon atoms. Therefore, inaccordance with the terminology used herein, a “hydrocarbon group”refers to a generalized group formed by removing one or more hydrogenatoms (as necessary for the particular group) from a hydrocarbon. A“hydrocarbyl group,” “hydrocarbylene group,” and “hydrocarbon group” canbe acyclic or cyclic groups, and/or can be linear or branched. A“hydrocarbyl group,” “hydrocarbylene group,” and “hydrocarbon group” caninclude rings, ring systems, aromatic rings, and aromatic ring systems,which contain only carbon and hydrogen. “Hydrocarbyl groups,”“hydrocarbylene groups,” and “hydrocarbon groups” include, by way ofexample, aryl, arylene, arene, alkyl, alkylene, alkane, cycloalkyl,cycloalkylene, cycloalkane, aralkyl, aralkylene, and aralkane groups,among other groups, as members.

The term “alkane” whenever used in this specification and claims refersto a saturated hydrocarbon compound. Other identifiers can be utilizedto indicate the presence of particular groups in the alkane (e.g.halogenated alkane indicates that the presence of one or more halogenatoms replacing an equivalent number of hydrogen atoms in the alkane).The term “alkyl group” is used herein in accordance with the definitionspecified by IUPAC: a univalent group formed by removing a hydrogen atomfrom an alkane. Similarly, an “alkylene group” refers to a group formedby removing two hydrogen atoms from an alkane (either two hydrogen atomsfrom one carbon atom or one hydrogen atom from two different carbonatoms). An “alkane group” is a general term that refers to a groupformed by removing one or more hydrogen atoms (as necessary for theparticular group) from an alkane. An “alkyl group,” “alkylene group,”and “alkane group” can be acyclic or cyclic groups, and/or can be linearor branched unless otherwise specified. Primary, secondary, and tertiaryalkyl group are derived by removal of a hydrogen atom from a primary,secondary, tertiary carbon atom, respectively, of an alkane. The n-alkylgroup can be derived by removal of a hydrogen atom from a terminalcarbon atom of a linear alkane. The groups RCH₂ (R≠H), R₂CH (R≠H), andR₃C (R≠H) are primary, secondary, and tertiary alkyl groups,respectively.

A cycloalkane is a saturated cyclic hydrocarbon, with or without sidechains, for example, cyclobutane. Unsaturated cyclic hydrocarbons havingone or more endocyclic double or one triple bond are called cycloalkenesand cycloalkynes, respectively. Cycloalkenes and cycloalkynes havingonly one, only two, only three, etc. . . . endocyclic double or triplebonds, respectively, can be identified by use of the term “mono,” “di,”“tri,: etc. . . . within the name of the cycloalkene or cycloalkyne.Cycloalkenes and cycloalkynes can further identify the position of theendocyclic double or triple bonds.

A “cycloalkyl group” is a univalent group derived by removing a hydrogenatom from a ring carbon atom of a cycloalkane. For example, a1-methylcyclopropyl group and a 2-methylcyclopropyl group areillustrated as follows.

Similarly, a “cycloalkylene group” refers to a group derived by removingtwo hydrogen atoms from a cycloalkane, at least one of which is a ringcarbon. Thus, a “cycloalkylene group” includes both a group derived froma cycloalkane in which two hydrogen atoms are formally removed from thesame ring carbon, a group derived from a cycloalkane in which twohydrogen atoms are formally removed from two different ring carbons, anda group derived from a cycloalkane in which a first hydrogen atom isformally removed from a ring carbon and a second hydrogen atom isformally removed from a carbon atom that is not a ring carbon. A“cycloalkane group” refers to a generalized group formed by removing oneor more hydrogen atoms (as necessary for the particular group and atleast one of which is a ring carbon) from a cycloalkane. It should benoted that according to the definitions provided herein, generalcycloalkane groups (including cycloalkyl groups and cycloalkylenegroups) include those having zero, one, or more than one hydrocarbylsubstituent groups attached to a cycloalkane ring carbon atom (e.g. amethylcyclopropyl group) and is member of the group of hydrocarbongroups. However, when referring to a cycloalkane group having aspecified number of cycloalkane ring carbon atoms (e.g. cyclopentanegroup or cyclohexane group, among others), the base name of thecycloalkane group having a defined number of cycloalkane ring carbonatoms refers to the unsubstituted cycloalkane group (including having nohydrocarbyl groups located on cycloalkane group ring carbon atom).Consequently, a substituted cycloalkane group having a specified numberof ring carbon atoms (e.g. substituted cyclopentane or substitutedcyclohexane, among others) refers to the respective group having one ormore substituent groups (including halogens, hydrocarbyl groups, orhydrocarboxy groups, among other substituent groups) attached to acycloalkane group ring carbon atom. When the substituted cycloalkanegroup having a defined number of cycloalkane ring carbon atoms is amember of the group of hydrocarbon groups (or a member of the generalgroup of cycloalkane groups), each substituent of the substitutedcycloalkane group having a defined number of cycloalkane ring carbonatoms is limited to hydrocarbyl substituent group. One can readilydiscern and select general groups, specific groups, and/or individualsubstituted cycloalkane group(s) having a specific number of ringcarbons atoms which can be utilized as member of the hydrocarbon group(or a member of the general group of cycloalkane groups).

The term “olefin” whenever used in this specification and claims refersto compounds that have at least one carbon-carbon double bond that isnot part of an aromatic ring or ring system. The term “olefin” includesaliphatic and aromatic, cyclic and acyclic, and/or linear and branchedcompounds having at least one carbon-carbon double bond that is not partof an aromatic ring or ring system unless specifically stated otherwise.The term “olefin,” by itself, does not indicate the presence or absenceof heteroatoms and/or the presence or absence of other carbon-carbondouble bonds unless explicitly indicated. Olefins having only one, onlytwo, only three, etc. . . . carbon-carbon double bonds can be identifiedby use of the term “mono,” “di,” “tri,” etc. . . . within the name ofthe olefin. The olefins can be further identified by the position of thecarbon-carbon double bond(s).

The term “alkene” whenever used in this specification and claims refersa linear or branched hydrocarbon olefin that has one or morecarbon-carbon double bonds. Alkenes having only one, only two, onlythree, etc. . . . such multiple bond can be identified by use of theterm “mono,” “di,” “tri,” etc. . . . within the name. For example,alkamonoenes, alkadienes, and alkatrienes refer to a linear or branchedhydrocarbon olefins having only one carbon-carbon double bond (generalformula C_(n)H_(2n)), only two carbon-carbon double bonds (generalformula C_(n)H_(2n−2)), and only three carbon-carbon double bonds(general formula C_(n)H_(2n−4)), respectively. Alkenes can be furtheridentified by the position of the carbon-carbon double bond(s). Otheridentifiers can be utilized to indicate the presence or absence ofparticular groups within an alkene. For example, a haloalkene refers toan alkene having one or more hydrogen atoms replaced with a halogenatom.

The term “alpha olefin” as used in this specification and claims refersto an olefin that has a carbon-carbon double bond between the first andsecond carbon atom of the longest contiguous chain of carbon atoms. Theterm “alpha olefin” includes linear and branched alpha olefins unlessexpressly stated otherwise. In the case of branched alpha olefins, abranch can be at the 2-position (a vinylidene) and/or the 3-position orhigher with respect to the olefin double bond. The term “vinylidene”whenever used in this specification and claims refers to an alpha olefinhaving a branch at the 2-position with respect to the olefin doublebond. By itself, the term “alpha olefin” does not indicate the presenceor absence of heteroatoms and/or the presence or absence of othercarbon-carbon double bonds unless explicitly indicated. The terms“hydrocarbon alpha olefin” or “alpha olefin hydrocarbon” refer to alphaolefin compounds containing only hydrogen and carbon.

The term “linear alpha olefin” as used herein refers to a linear olefinhaving a carbon-carbon double bond between the first and second carbonatom. The term “linear alpha olefin” by itself does not indicate thepresence or absence of heteroatoms and/or the presence or absence ofother carbon-carbon double bonds, unless explicitly indicated. The terms“linear hydrocarbon alpha olefin” or “linear alpha olefin hydrocarbon”refers to linear alpha olefin compounds containing only hydrogen andcarbon.

The term “normal alpha olefin” whenever used in this specification andclaims refers to a linear hydrocarbon mono-olefin having a carbon carbondouble bond between the first and second carbon atom. It is noted that“normal alpha olefin” is not synonymous with “linear alpha olefin” asthe term “linear alpha olefin” can include linear olefinic compoundshaving a double bond between the first and second carbon atoms andhaving heteroatoms and/or additional double bonds.

The term “consists essentially of normal alpha olefin(s),” or variationsthereof, whenever used in this specification and claims refers tocommercially available normal alpha olefin product(s). The commerciallyavailable normal alpha olefin product can contain non-normal alphaolefin impurities such as vinylidenes, internal olefins, branched alphaolefins, paraffins, and diolefins, among other impurities, which are notremoved during the normal alpha olefin production process. One readilyrecognizes that the identity and quantity of the specific impuritiespresent in the commercial normal alpha olefin product will depend uponthe source of commercial normal alpha olefin product. Consequently, theterm “consists essentially of normal alpha olefins” and its variants isnot intended to limit the amount/quantity of the non-linear alpha olefincomponents any more stringently than the amounts/quantities present in aparticular commercial normal alpha olefin product unless explicitlystated.

A “heterocyclic compound” is a cyclic compound having at least twodifferent elements as ring member atoms. For example, heterocycliccompounds can comprise rings containing carbon and nitrogen (forexample, tetrahydropyrrole), carbon and oxygen (for example,tetrahydrofuran), or carbon and sulfur (for example,tetrahydrothiophene), among others. Heterocyclic compounds andheterocyclic groups can be either aliphatic or aromatic.

A “heterocyclyl group” is a univalent group formed by removing ahydrogen atom from a heterocyclic ring or ring system carbon atom of aheterocyclic compound. By specifying that the hydrogen atom is removedfrom a heterocyclic ring or ring system carbon atom, a “heterocyclylgroup” is distinguished from a “cycloheteryl group,” in which a hydrogenatom is removed from a heterocyclic ring or ring system heteroatom. Forexample, a pyrrolidin-2-yl group illustrated below is one example of a“heterocyclyl group,” and a pyrrolidin-1-yl group illustrated below isone example of a “cycloheteryl” group.”

Similarly, a “heterocyclylene group” or more simply, a “heterocyclenegroup,” refers to a group formed by removing two hydrogen atoms from aheterocyclic compound, at least one of which is from a heterocyclic ringor ring system carbon. Thus, in a “heterocyclylene group,” at least onehydrogen is removed from a heterocyclic ring or ring system carbon atom,and the other hydrogen atom can be removed from any other carbon atom,including for example, the same heterocyclic ring or ring system carbonatom, a different heterocyclic ring or ring system ring carbon atom, ora non-ring carbon atom. A “heterocyclic group” refers to a generalizedgroup formed by removing one or more hydrogen atoms (as necessary forthe particular group and at least one of which is a heterocyclic ringcarbon atom) from a heterocyclic compound. Generally, a heterocycliccompound can be aliphatic or aromatic unless otherwise specified.

A “cycloheteryl group” is a univalent group formed by removing ahydrogen atom from a heterocyclic ring or ring system heteroatom of aheterocyclic compound, as illustrated. By specifying that the hydrogenatom is removed from a heterocyclic ring or ring system heteroatom andnot from a ring carbon atom, a “cycloheteryl group” is distinguishedfrom a “heterocyclyl group” in which a hydrogen atom is removed from aheterocyclic ring or ring system carbon atom. Similarly, a“cycloheterylene group” refers to a group formed by removing twohydrogen atoms from an heterocyclic compound, at least one of which isremoved from a heterocyclic ring or ring system heteroatom of theheterocyclic compound; the other hydrogen atom can be removed from anyother atom, including for example, a heterocyclic ring or ring systemring carbon atom, another heterocyclic ring or ring system heteroatom,or a non-ring atom (carbon or heteroatom). A “cyclohetero group” refersto a generalized group formed by removing one or more hydrogen atoms (asnecessary for the particular group and at least one of which is from aheterocyclic ring or ring system heteroatom) from a heterocycliccompound.

An aliphatic compound is an acyclic or cyclic, saturated or unsaturatedcarbon compound, excluding aromatic compounds. Thus, an aliphaticcompound is an acyclic or cyclic, saturated or unsaturated carboncompound, excluding aromatic compounds; that is, an aliphatic compoundis a non-aromatic organic compound. An “aliphatic group” is ageneralized group formed by removing one or more hydrogen atoms (asnecessary for the particular group) from the carbon atom of an aliphaticcompound. Thus, an aliphatic compound is an acyclic or cyclic, saturatedor unsaturated carbon compound, excluding aromatic compounds. That is,an aliphatic compound is a non-aromatic organic compound. Aliphaticcompounds and therefore aliphatic groups can contain organic functionalgroup(s) and/or atom(s) other than carbon and hydrogen.

An aromatic compound is a compound containing a cyclically conjugateddouble bond system that follows the Hückel (4n+2) rule and contains(4n+2) pi-electrons, where n is an integer from 1 to 5. Aromaticcompounds include “arenes” (hydrocarbon aromatic compounds) and“heteroarenes,” also termed “hetarenes” (heteroaromatic compoundsformally derived from arenes by replacement of one or more methine (—C═)carbon atoms of the cyclically conjugated double bond system with atrivalent or divalent heteroatoms, in such a way as to maintain thecontinuous pi-electron system characteristic of an aromatic system and anumber of out-of-plane pi-electrons corresponding to the Hückel rule(4n+2). While arene compounds and heteroarene compounds are mutuallyexclusive members of the group of aromatic compounds, a compound thathas both an arene group and a heteroarene group are generally considereda heteroarene compound. Aromatic compounds, arenes, and heteroarenes canbe monocyclic (e.g., benzene, toluene, furan, pyridine, methylpyridine)or polycyclic unless otherwise specified. Polycyclic aromatic compounds,arenes, and heteroarenes, include, unless otherwise specified, compoundswherein the aromatic rings can be fused (e.g., naphthalene, benzofuran,and indole), compounds where the aromatic groups can be separate andjoined by a bond (e.g., biphenyl or 4-phenylpyridine), or compoundswhere the aromatic groups are joined by a group containing linking atoms(e.g., carbon—the methylene group in diphenylmethane; oxygen—diphenylether; nitrogen—triphenyl amine; among others linking groups). Asdisclosed herein, the term “substituted” can be used to describe anaromatic group, arene, or heteroarene wherein a non-hydrogen moietyformally replaces a hydrogen in the compound, and is intended to benon-limiting.

An “aromatic group” refers to a generalized group formed by removing oneor more hydrogen atoms (as necessary for the particular group and atleast one of which is an aromatic ring carbon atom) from an aromaticcompound. For a univalent “aromatic group,” the removed hydrogen atommust be from an aromatic ring carbon. For an “aromatic group” formed byremoving more than one hydrogen atom from an aromatic compound, at leastone hydrogen atom must be from an aromatic hydrocarbon ring carbon.Additionally, an “aromatic group” can have hydrogen atoms removed fromthe same ring of an aromatic ring or ring system (e.g., phen-1,4-ylene,pyridin-2,3-ylene, naphth-1,2-ylene, and benzofuran-2,3-ylene), hydrogenatoms removed from two different rings of a ring system (e.g.,naphth-1,8-ylene and benzofuran-2,7-ylene), or hydrogen atoms removedfrom two isolated aromatic rings or ring systems (e.g.,bis(phen-4-ylene)methane).

An arene is an aromatic hydrocarbon, with or without side chains (e.g.benzene, toluene, or xylene, among others. An “aryl group” is a groupderived from the formal removal of a hydrogen atom from an aromatic ringcarbon of an arene. It should be noted that the arene can contain asingle aromatic hydrocarbon ring (e.g., benzene, or toluene), containfused aromatic rings (e.g., naphthalene or anthracene), and/or containone or more isolated aromatic rings covalently linked via a bond (e.g.,biphenyl) or non-aromatic hydrocarbon group(s) (e.g., diphenylmethane).One example of an “aryl group” is ortho-tolyl (o-tolyl), the structureof which is shown here.

Similarly, an “arylene group” refers to a group formed by removing twohydrogen atoms (at least one of which is from an aromatic ring carbon)from an arene. An “arene group” refers to a generalized group formed byremoving one or more hydrogen atoms (as necessary for the particulargroup and at least one of which is an aromatic ring carbon) from anarene. However, if a group contains separate and distinct arene andheteroarene rings or ring systems (e.g. the phenyl and benzofuranmoieties in 7-phenylbenzofuran) its classification depends upon theparticular ring or ring system from which the hydrogen atom was removed,that is, an arene group if the removed hydrogen came from the aromatichydrocarbon ring or ring system carbon atom (e.g. the 2 carbon atom inthe phenyl group of 6-phenylbenzofuran) and a heteroarene group if theremoved hydrogen carbon came from a heteroaromatic ring or ring systemcarbon atom (e.g. the 2 or 7 carbon atom of the benzofuran group or6-phenylbenzofuran). It should be noted that according the definitionsprovided herein, general arene groups (including an aryl group and anaraylene group) include those having zero, one, or more than onehydrocarbyl substituent groups located on an aromatic hydrocarbon ringor ring system carbon atom (e.g. a toluene group or a xylene group,among others) and is a member of the group of hydrocarbon groups.However, a phenyl group (or phenylene group) and/or a naphthyl group (ornaphthylene group) refer to the specific unsubstituted arene groups(including no hydrocarbyl group located on an aromatic hydrocarbon ringor ring system carbon atom). Consequently, a substituted phenyl group orsubstituted naphthyl group refers to the respective arene group havingone or more substituent groups (including halogens, hydrocarbyl groups,or hydrocarboxy groups, among others) located on an aromatic hydrocarbonring or ring system carbon atom. When the substituted phenyl groupand/or substituted naphtyl group is a member of the group of hydrocarbongroups (or a member of the general group of arene groups), eachsubstituent is limited to a hydrocarbyl substituent group. One havingordinary skill in the art can readily discern and select general phenyland/or naphthyl groups, specific phenyl and/or naphthyl groups, and/orindividual substituted phenyl or substituted naphthyl groups which canbe utilized as a member of the group of hydrocarbon groups (or a memberof the general group of arene groups).

A heteroarene is an aromatic compound, with or without side chains,having a heteroatom within the aromatic ring or aromatic ring system(e.g. pyridene, indole, or benzofuran, among others). A “heteroarylgroup” is a class of “heterocyclyl group” and is a univalent groupformed by removing a hydrogen atom from a heteroaromatic ring or ringsystem carbon atom of a heteroarene compound. By specifying that thehydrogen atom is removed from a ring carbon atom, a “heteroaryl group”is distinguished from an “arylheteryl group,” in which a hydrogen atomis removed from a heteroaromatic ring or ring system heteroatom. Forexample, an indol-2-yl group illustrated below is one example of a“heteroaryl group,” and an indol-1-yl group illustrated below is oneexample of an “arylheteryl” group.”

Similarly, a “heteroarylene group” refers to a group formed by removingtwo hydrogen atoms from a heteroarene compound, at least one of which isfrom a heteroarene ring or ring system carbon atom. Thus, in a“heteroarylene group,” at least one hydrogen is removed from aheteroarene ring or ring system carbon atom, and the other hydrogen atomcan be removed from any other carbon atom, including for example, aheteroarene ring or ring system carbon atom, or a non-heteroarene ringor ring system atom. A “heteroarene group” refers to a generalized groupformed by removing one or more hydrogen atoms (as necessary for theparticular group and at least one of which is a heteroarene ring or ringsystem carbon atom) from a heteroarene compound. If a hydrogen atom isremoved from a heteroaromatic ring or ring system heteroatom and from aheteroaromatic ring or ring system carbon atom or an aromatichydrocarbon ring or ring system carbon atom, the group is classified asan “arylheterylene group” or an “arylhetero group.”

An “arylheteryl group” is a class of “cycloheteryl group” and is aunivalent group formed by removing a hydrogen atom from a heteroaromaticring or ring system heteroatom, as illustrated. By specifying that thehydrogen atom is removed from of a heteroaromatic ring or ring systemheteroatom and not from a heteroaromatic ring or ring system carbonatom, an “arylheteryl group” is distinguished from a “heteroaryl group”in which a hydrogen atom is removed from a heteroaromatic ring or a ringsystem carbon atom. Similarly, an “arylheterylene group” refers to agroup formed by removing two hydrogen atoms from a heteroaryl compound,at least one of which is removed from a heteroaromatic ring or ringsystem heteroatom of the heteroaryl compound; the other hydrogen atomcan be removed from any other atom, including for example, aheteroaromatic ring or ring system carbon atom, another heteroaromaticring or ring system heteroatom, or a non-ring atom (carbon orheteroatom) from a heteroaromatic compound. An “arylhetero group” refersto a generalized group formed by removing one or more hydrogen atoms (asnecessary for the particular group and at least one of which is from aheteroaromatic ring or ring system) heteroatom from a heteroarenecompound.

An “aralkyl group” is an aryl-substituted alkyl group having a freevalance at a non-aromatic carbon atom (e.g. a benzyl group, or a2-phenyleth-1yl group, among others). Similarly, an “aralkylene group”is an aryl-substituted alkylene group having two free valencies at asingle non-aromatic carbon atom or a free valence at two non-aromaticcarbon atoms while an “aralkane group” is a generalized aryl-substitutedalkane group having one or more free valencies at a non-aromatic carbonatom(s). A “heteroaralkyl group” is a heteroaryl-substituted alkyl grouphaving a free valence at a non-heteroaromatic ring or ring system carbonatom. Similarly a “heteroaralkylene group” is a heteroaryl-substitutedalkylene group having two free valencies at a single non-heteroaromaticring or ring system carbon atom or a free valence at twonon-heteroaromatic ring or ring system carbon atoms while a“heteroaralkane group” is a generalized aryl-substituted alkane grouphaving one or more free valencies at a non-heteroaromatic ring or ringsystem carbon atom(s). It should be noted that according the definitionsprovided herein, general aralkane groups include those having zero, one,or more than one hydrocarbyl substituent groups located on an aralkanearomatic hydrocarbon ring or ring system carbon atom and is a member ofthe group of hydrocarbon groups. However, specific aralkane groupsspecifying a particular aryl group (e.g. the phenyl group in a benzylgroup or a 2-phenylethyl group, among others) refer to the specificunsubstituted aralkane groups (including no hydrocarbyl group located onthe aralkane aromatic hydrocarbon ring or ring system carbon atom).Consequently, a substituted aralkane group specifying a particular arylgroup refers to a respective aralkane group having one or moresubstituent groups (including halogens, hydrocarbyl groups, orhydrocarboxy groups, among others). When the substituted aralkane groupspecifying a particular aryl group is a member of the group ofhydrocarbon groups (or a member of the general group of aralkanegroups), each substituent is limited to a hydrocarbyl substituent group.One can readily discern and select substituted aralkane groupsspecifying a particular aryl group which can be utilized as a member ofthe group of hydrocarbon groups (or a member of the general group ofaralkane groups).

A “halide” has its usual meaning; therefore, examples of halides includefluoride, chloride, bromide, and iodide.

An “organoheteryl group” is a univalent group containing carbon, whichare thus organic, but which have their free valence at an atom otherthan carbon. Thus, organoheteryl and organyl groups are complementaryand mutually exclusive. Organoheteryl groups can be cyclic or acyclic,and/or aliphatic or aromatic, and thus encompass aliphatic “cycloheterylgroups” (e.g. pyrrolidin-1-yl or morpholin-1-yl, among others), aromatic“arylheteryl groups” (e.g. pyrrol-1-yl or indol-1-yl, among others), andacyclic groups (e.g. organylthio, trihydrocarbylsilyl, aryloxy, oralkoxy, among others). Similarly, an “organoheterylene group” is adivalent group containing carbon and at least one heteroatom having twofree valencies, at least one of which is at a heteroatom. An“organohetero group” is a generalized group containing carbon and atleast one heteroatom having one or more free valencies (as necessary forthe particular group and at least one of which is at a heteroatom) froman organohetero compound.

An “organoaluminum compound,” is used to describe any compound thatcontains an aluminum-carbon bond. Thus, organoaluminum compounds includehydrocarbyl aluminum compounds such as trialkyl-, dialkyl-, ormonoalkylaluminum compounds; hydrocarbyl alumoxane compounds, andaluminate compounds which contain an aluminum-organyl bond such astetrakis(p-tolyl)aluminate salts.

Within this disclosure the normal rules of organic nomenclature willprevail. For instance, when referencing substituted compounds or groups,references to substitution patterns are taken to indicate that theindicated group(s) is (are) located at the indicated position and thatall other non-indicated positions are hydrogen. For example, referenceto a 4-substituted phenyl group indicates that there is a non-hydrogensubstituent located at the 4 position and hydrogens located at the 2, 3,5, and 6 positions. By way of another example, reference to a3-substituted naphth-2-yl indicates that there is a non-hydrogensubstituent located at the 3 position and hydrogens located at the 1, 4,5, 6, 7, and 8 positions. References to compounds or groups havingsubstitutions at positions in addition to the indicated position will bereferenced using comprising or some other alternative language. Forexample, a reference to a phenyl group comprising a substituent at the 4position refers to a group having a non-hydrogen atom at the 4 positionand hydrogen or any non-hydrogen group at the 2, 3, 5, and 6 positions.

The term “reactor effluent,” and it derivatives (e.g. oligomerizationreactor effluent) generally refers to all the material which exits thereactor. The term “reactor effluent,” and its derivatives, can also beprefaced with other descriptors that limit the portion of the reactoreffluent being referenced. For example, while the term “reactoreffluent” would refer to all material exiting the reactor (e.g. productand solvent or diluent, among others), the term “olefin reactoreffluent” refers to the effluent of the reactor which contains an olefin(i.e. carbon-carbon) double bond.

The term “oligomerization,” and its derivatives, refers to processeswhich produce a mixture of products containing at least 70 weightpercent products containing from 2 to 30 monomer units. Similarly, an“oligomer” is a product that contains from 2 to 30 monomer units whilean “oligomerization product” includes all product made by the“oligomerization” process including the “oligomers” and products whichare not “oligomers” (e.g. product which contain more than 30 monomerunits). It should be noted that the monomer units in the “oligomer” or“oligomerization product” do not have to be the same. For example, an“oligomer” or “oligomerization product” of an “oligomerization” processusing ethylene and propylene as monomers can contain both ethyleneand/or propylene units.

The term “trimerization,” and it derivatives, refers to a process whichproduces a mixture of products containing at least 70 weight percentproducts containing three and only three monomer units. A “trimer” is aproduct which contains three and only three monomer units while a“trimerization product” includes all products made by the trimerizationprocess including trimers and products which are not trimers (e.g.dimers or tetramers). Generally, an olefin trimerization reduces thenumber of olefinic bonds, i.e., carbon-carbon double bonds, by two whenconsidering the number of olefin bonds in the monomer units and thenumber of olefin bonds in the trimer. It should be noted that themonomer units in the “trimer” or “trimerization product” do not have bethe same. For example, a “trimer” of a “trimerization” process usingethylene and butene as monomers can contain ethylene and/or butenemonomer units. That is to say the “trimer” will include C₆, C₈, C₁₀, andC₁₂ products. In another example, a “trimer” of a “trimerization”process using ethylene as the monomer can contain ethylene monomerunits. It should also be noted that a single molecule can contain twomonomer units. For example, dienes such as 1,3-butadiene and1,4-pentadiene have two monomer units within one molecule.

The term “tetramerization,” and it derivatives, refers to a processwhich produces a mixture of products containing at least 70 weightpercent products containing four and only four monomer units. A“tetramer” is a product which contains four and only four monomer unitswhile a “tetramerization product” includes all products made by thetetramerization process including tetramers and products which are nottetramers (e.g. dimers or trimer). Generally, an olefin tetramerizationreduces the number of olefinic bonds, i.e., carbon-carbon double bonds,by three when considering the number of olefin bonds in the monomerunits and the number of olefin bonds in the tetramer. It should be notedthat the monomer units in the “tetramer” or “tetramerization product” donot have be the same. For example, a “tetramer” of a “tetramerization”process using ethylene and butene as monomers can contain ethyleneand/or butene monomer units. In an example, a “tetramer” of a“tetramerization” process using ethylene as the monomer can containethylene monomer units. It should also be noted that a single moleculecan contain two monomer units. For example, dienes such as 1,3-butadieneand 1,4-pentadiene have two monomer units within one molecule.

The term “trimerization and tetramerization,” and it derivatives, refersto a process which produces a mixture of products containing at least 70weight percent products containing three and/or four and only threeand/or four monomer units. A “trimerization and tetramerization product”includes all products made by the “trimerization and tetramerization”process including trimers, tetramers, and products which are not trimersor tetramers (e.g. dimers). In an example, a “trimerization andtetramerization” process using ethylene as the monomer produces amixture of products containing at least 70 weight percent hexene and/oroctene.

The term or variation of the terms an “oligomerized product having Xcarbon atoms” and “C_(X) oligomer product,” wherein X can be anypositive non-zero integer, refers to materials produced by monomeroligomerization which have X carbon atoms. Thus, the term oligomerizedproduct having X carbon atoms excludes materials having X carbon atomswhich were not produced by the oligomerization (e.g. solvent). Theseterms can also include other descriptive words (e.g. olefin, liquid, andmixture, among others) without detracting from the essence of the termreferring to materials having X carbon atoms, produced by monomeroligomerization, and fitting the additional descriptive terms.

This disclosure encompasses N²-phosphinyl formamidine compounds, methodsfor making N²-phosphinyl formamidine compounds, metal salt complexescomprising N²-phosphinyl formamidine compounds, methods of making metalsalt complexes comprising N²-phosphinyl formamidine compounds, catalystsystems comprising N²-phosphinyl formamidine compounds, methods ofmaking catalyst systems comprising N²-phosphinyl formamidine compounds,and methods of oligomerizing olefins utilizing catalysts systemcomprising N²-phosphinyl formamidine compounds, among other aspects andembodiments. These aspects of this disclosure are further describedherein. While these aspects can be disclosed under these headings, theheading does not limit the disclosure found therein. Additionally thevarious aspects and embodiments disclosed herein can be combined in anymanner.

N²-Phosphinyl Formamidine Compounds

In an aspect, the compounds encompassed by the present disclosureinclude an N²-phosphinyl formamidine compound. Generally, theN²-phosphinyl formamidine compounds encompassed by this disclosure cancomprise an N²-phosphinyl formamidine group; or alternatively, comprisetwo N²-phosphinyl formamidine groups. In an embodiment, theN²-phosphinyl formamidine compounds comprise only one N²-phosphinylformamidine group; or alternatively, comprise only two N²-phosphinylformamidine groups. In an embodiment, the compounds, regardless of thenumber of N²-phosphinyl formamidine groups, or structure, can benon-metallic (i.e., a non-metallic N²-phosphinyl formamidine compound ora non-metallic compound having an N²-phosphinyl formamidine group). Insome embodiments, the formamidine group of the N²-phosphinyl formamidinecompounds can be an acyclic formamidine group (a formamidine groupwherein the two nitrogen atoms and the central carbon atom of the aminegroup are not contained in a ring).

In an aspect, the N²-phosphinyl formamidine compound can have StructureNPF1 or NPF2, alternatively, Structure NPF1; or alternatively, StructureNPF2.

R¹, R³, R⁴, and R⁵ within N²-phosphinyl formamidine compound StructuresNPF1 and/or NPF2 are independently described herein and can be utilizedwithout limitation to further describe the N²-phosphinyl formamidinecompounds having Structures NPF1 and/or NPF2. In other embodiments, theN²-phosphinyl formamidine compounds can have any specific structuredisclosed herein.

Generally, R¹ can be an organyl group; alternatively, an organyl groupconsisting essentially of inert functional groups; or alternatively, ahydrocarbyl group. In an embodiment, R¹ can be a C₁ to C₃₀ organylgroup; alternatively, a C₁ to C₂₀ organyl group; alternatively, a C₁ toC₁₅ organyl group; alternatively, a C₁ to C₁₀ organyl group; oralternatively, a C₁ to C₅ organyl group. In an embodiment, R¹ can be aC₁ to C₃₀ organyl group consisting essentially of inert functionalgroups; alternatively, a C₁ to C₂₀ organyl group consisting essentiallyof inert functional groups; alternatively, a C₁ to C₁₅ organyl groupconsisting essentially of inert functional groups; alternatively, a C₁to C₁₀ organyl group consisting essentially of inert functional groups;or alternatively, a C₁ to C₅ organyl group consisting essentially ofinert functional groups. In an embodiment, R¹ can be a C₁ to C₃₀hydrocarbyl group; alternatively, a C₁ to C₂₀ hydrocarbyl group;alternatively, a C₁ to C₁₅ hydrocarbyl group; alternatively, a C₁ to C₁₀hydrocarbyl group; or alternatively, a C₁ to C₅ hydrocarbyl group. Inyet other embodiments, R¹ can be a C₃ to C₃₀ aromatic group;alternatively, a C₃ to C₂₀ aromatic group; alternatively, a C₃ to C₁₅aromatic group; or alternatively, a C₃ to C₁₀ aromatic group.

In an aspect, R¹ can be a C₁ to C₃₀ alkyl group, a C₄ to C₃₀ cycloalkylgroup, a C₄ to C₃₀ substituted cycloalkyl group, a C₆ to C₃₀ aryl group,or a C₆ to C₃₀ substituted aryl group; alternatively, a C₄ to C₃₀cycloalkyl group or a C₄ to C₃₀ substituted cycloalkyl group;alternatively, a C₆ to C₃₀ aryl group or a C₆ to C₃₀ substituted arylgroup; alternatively, a C₁ to C₃₀ alkyl group; alternatively, a C₄ toC₃₀ cycloalkyl group; alternatively, a C₄ to C₃₀ substituted cycloalkylgroup; alternatively, a C₆ to C₃₀ aryl group; or alternatively, a C₆ toC₃₀ substituted aryl group. In an embodiment, R¹ can be a C₁ to C₁₅alkyl group, a C₄ to C₂₀ cycloalkyl group, a C₄ to C₂₀ substitutedcycloalkyl group, a C₆ to C₂₀ aryl group, or a C₆ to C₂₀ substitutedaryl group; alternatively, a C₄ to C₂₀ cycloalkyl group or a C₄ to C₂₀substituted cycloalkyl group; alternatively, a C₆ to C₂₀ aryl group or aC₆ to C₂₀ substituted aryl group; alternatively, a C₁ to C₁₅ alkylgroup; alternatively, a C₄ to C₂₀ cycloalkyl group; alternatively, a C₄to C₂₀ substituted cycloalkyl group; alternatively, a C₆ to C₂₀ arylgroup; or alternatively, a C₆ to C₂₀ substituted aryl group. In otherembodiments, R¹ can be a C₁ to C₁₀ alkyl group, a C₄ to C₁₅ cycloalkylgroup, a C₄ to C₁₅ substituted cycloalkyl group, a C₆ to C₁₅ aryl group,or a C₆ to C₁₅ substituted aryl group; alternatively, a C₄ to C₁₅cycloalkyl group or a C₄ to C₁₅ substituted cycloalkyl group;alternatively, a C₆ to C₁₅ aryl group or a C₆ to C₁₅ substituted arylgroup; alternatively, a C₁ to C₁₀ alkyl group; alternatively, a C₄ toC₁₅ cycloalkyl group; alternatively, a C₄ to C₁₅ substituted cycloalkylgroup; alternatively, a C₆ to C₁₅ aryl group; or alternatively, a C₆ toC₁₅ substituted aryl group; or alternatively, a C₃ to C₁₅ heteroarylgroup. In further embodiments, R¹ can be a C₁ to C₅ alkyl group.

In an embodiment, R¹ can be a methyl group, an ethyl group, a propylgroup, a butyl group, a pentyl group, a hexyl group, a heptyl group, anoctyl group, a nonyl group, or a decyl group. In some embodiments, R¹can be a methyl group, an ethyl group, an n-propyl group, an iso-propylgroup, an n-butyl group, an iso-butyl group, a sec-butyl group, atert-butyl group, an n-pentyl group, an iso-pentyl group, a sec-pentylgroup, or a neopentyl group; alternatively, a methyl group, an ethylgroup, an iso-propyl group, a tert-butyl group, or a neopentyl group;alternatively, a methyl group; alternatively, an ethyl group;alternatively, an n-propyl group; alternatively, an iso-propyl group;alternatively, a tert-butyl group; or alternatively, a neopentyl group.In some embodiments, the alkyl groups which can be utilized as R¹ can besubstituted. Each substituent of a substituted alkyl group independentlycan be a halogen or a hydrocarboxy group; alternatively, a halogen; oralternatively, a hydrocarboxy group. Halogens and hydrocarboxy groups(general and specific) that can be utilized as substituents areindependently disclosed herein and can be utilized without limitation tofurther describe the substituted alkyl group which can be utilized asR¹.

In an embodiment, R¹ can be a cyclobutyl group, a substituted cyclobutylgroup, a cyclopentyl group, a substituted cyclopentyl group, acyclohexyl group, a substituted cyclohexyl group, a cycloheptyl group, asubstituted cycloheptyl group, a cyclooctyl group, or a substitutedcyclooctyl group. In some embodiments, R¹ can be a cyclopentyl group, asubstituted cyclopentyl group, a cyclohexyl group, or a substitutedcyclohexyl group. In other embodiments, R¹ can be a cyclopentyl group ora substituted cyclopentyl group; or alternatively, a cyclohexyl group ora substituted cyclohexyl group. In further embodiments, R¹ can be acyclopentyl group; alternatively, a substituted cyclopentyl group; acyclohexyl group; or alternatively, a substituted cyclohexyl group.Substituents (general and specific) are independently disclosed hereinand can be utilized without limitation to further describe thesubstituted cycloalkyl group which can be utilized as R¹.

In an aspect, R¹ can have Structure G1:

wherein the undesignated valency is attached to the N¹ nitrogen atom ofthe N²-phosphinyl formamidine group. Generally, R^(11c), R^(12c),R^(13c), R^(14c), and R^(15c) can independently be hydrogen or anon-hydrogen substituent, and n can be an integer from 1 to 5. In anembodiment wherein R¹ has Structure G1, R^(11c), R^(13c), R^(14c), andR^(15c) can be hydrogen and R^(12c) can be any non-hydrogen substituentdisclosed herein; or alternatively, R^(11c), R^(13c), and R^(15c) can behydrogen and R^(12c) and R^(14c) independently can be any non-hydrogensubstituent disclosed herein. In an embodiment, n can be an integer from1 to 4; or alternatively, from 2 to 4. In other embodiments, n can be 2or 3; alternatively, 2; or alternatively 3. Substituents (general andspecific) are independently disclosed herein and can be utilized withoutlimitation to further describe a non-hydrogen substituent which can beutilized without limitation as R^(11c), R^(12c), R^(13c), R^(14c),and/or R^(15c) for the R¹ group having Structure G1.

In an embodiment wherein R¹ has Structure G1, R^(11c), R^(13c), R^(14c),and R^(15c) can be hydrogen and R^(12c) can be any non-hydrogensubstituent indicated herein; or alternatively, R^(11c), R^(13c), andR^(15c) can be hydrogen and R^(12c) and R^(14c) can be any non-hydrogensubstituent indicated herein. In some embodiments, wherein R¹ hasStructure G1, R^(11c), R^(13c), R^(14c), and R^(15c) can be hydrogen andR^(12c) can be any alkyl group, alkoxy group, or halogen indicatedherein; or alternatively, R^(11c), R^(13c), and R^(15c) can be hydrogenand R^(12c) and R^(14c) can be any alkyl group, alkoxy group, or halogenindicated herein. In other embodiments, wherein R¹ has Structure G1,R^(11c), R^(13c), R^(14c), and R^(15c) can be hydrogen and R^(12c) canbe any alkyl group substituent indicated herein; or alternatively,R^(11c), R^(13c), and R^(15c) can be hydrogen and R^(12c) and R^(14c)can be any alkyl group substituent indicated herein. In anotherembodiment wherein R¹ has Structure G1, R^(11c), R^(12c), R^(13c),R^(14c), and R^(15c) can be hydrogen. In an embodiment, R^(11c),R^(12c), R^(13c), R^(14c), and R^(15c) independently can be hydrogen, oran alkyl group; alternatively, R^(11c), R^(12c), and R^(14c) can behydrogen and R^(13c) and R^(15c) can be are alkyl groups; oralternatively, R^(11c) can be hydrogen and R^(12c), R^(13c), R^(14c),and R^(15c) can be alkyl groups. Specific substituent halogens,hydrocarbyl groups, hydrocarboxy groups, alkyl group, and alkoxy groupsare independently disclosed herein and can be utilized withoutlimitation to further describe the R¹ group having Structure G1.

In an aspect, R¹ can be a phenyl group, a substituted phenyl group, anaphthyl group, or a substituted naphthyl group; alternatively, a phenylgroup or a substituted phenyl group; alternatively, a naphthyl group ora substituted naphthyl group; alternatively, a phenyl group or anaphthyl group; or alternatively, a substituted phenyl group or asubstituted naphthyl group. In some embodiments, R¹ independently can bea phenyl group; alternatively, a substituted phenyl group;alternatively, a naphthyl group; or alternatively, a substitutednaphthyl group. In an embodiment, the R¹ substituted phenyl group can bea 2-substituted phenyl group, a 3-substituted phenyl group, a4-substituted phenyl group, a 2,4 disubstituted phenyl group, a2,6-disubstituted phenyl group, 3,5-disubstituted phenyl group, or a2,4,6-trisubstituted phenyl group. In other embodiments, the R¹substituted phenyl group can be a 2-substituted phenyl group, a4-substituted phenyl group, a 2,4-disubstituted phenyl group, a2,6-disubstituted phenyl group, or a 2,4,6-trisubstituted phenyl group;alternatively, a 2-substituted phenyl group, a 4-substituted phenylgroup, a 2,4-disubstituted phenyl group, or a 2,6-disubstituted phenylgroup; alternatively, a 3-substituted phenyl group or a3,5-disubstituted phenyl group; alternatively, a 2 substituted phenylgroup or a 4-substituted phenyl group; alternatively, a2,4-disubstituted phenyl group, a 2,6-disubstituted phenyl group, or a2,4,6-trisubstituted phenyl group; alternatively, a 2,6-di-substitutedphenyl group or a 2,4,6-trisubstituted phenyl group; alternatively, a2,4-disubstituted phenyl group or a 2,6-disubstituted phenyl group;alternatively, a 2-substituted phenyl group; alternatively, a 3substituted phenyl group; alternatively, a 4-substituted phenyl group;alternatively, a 2,4-disubstituted phenyl group; alternatively, a2,6-disubstituted phenyl group; alternatively, a 3,5-disubstitutedphenyl group; or alternatively, a 2,4,6-trisubstituted phenyl group.Substituents (general and specific) are independently disclosed hereinand can be utilized without limitation to further describe anysubstituted phenyl group which can be utilized as R¹.

In an embodiment, R¹ can be a naphth-1-yl group, a substitutednaphth-1-yl group, a naphth-2-yl group, or a substituted naphth-2-ylgroup. In some embodiments, R¹ can be a naphth-1-yl group or asubstituted naphth-1-yl group; alternatively, a naphth-2-yl group or asubstituted naphth-2-yl group; alternatively, a naphth-1-yl group;alternatively, a substituted naphth-1-yl group; alternatively, anaphth-2-yl group; or alternatively, a substituted naphth-2-yl group. Inother embodiments, R¹ can be a 2 substituted naphth-1-yl group, a3-substituted naphth-1-yl group, a 4-substituted naphth-1-yl group, or a8-substituted naphth-1-yl group; alternatively, a 2-substitutednaphth-1-yl group; alternatively, a 3 substituted naphth-1-yl group;alternatively, a 4-substituted naphth-1-yl group; or alternatively, a 8substituted naphth-1-yl group. In further embodiments, R¹ can be a1-substituted naphth-2-yl group, a 3 substituted naphth-2-yl group, a4-substituted naphth-2-yl group, or a 1,3-disubstituted naphth-2-ylgroup; alternatively, a 1-substituted naphth-2-yl group; alternatively,a 3-substituted naphth-2-yl group; alternatively, a 4-substitutednaphth-2-yl group; or alternatively, a 1,3-disubstituted naphth-2-ylgroup. Substituents (general and specific) are independently disclosedherein can be utilized without limitation to further describe anysubstituted naphthyl groups which can be utilized as R¹.

In an aspect, the R¹ can have Structure G2:

wherein the undesignated valency is attached to the N¹ nitrogen atom ofthe N²-phosphinyl formamidine group. Generally, R¹², R¹³, R¹⁴, R¹⁵, andR¹⁶ independently can be hydrogen or a non-hydrogen substituent. In anembodiment wherein R¹ has Structure G2, R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ canbe hydrogen, R¹³, R¹⁴, R¹⁵ and R¹⁶ can be hydrogen and R¹² can be anon-hydrogen substituent, R¹², R¹⁴, R¹⁵, and R¹⁶ can be hydrogen and R¹³can be a non-hydrogen substituent, R¹², R¹³, R¹⁵, and R¹⁶ can behydrogen and R¹⁴ can be a non-hydrogen substituent, R¹³, R¹⁵, and R¹⁶can be hydrogen and R¹² and R¹⁴ can be non-hydrogen substituents, R¹³,R¹⁴, and R¹⁵ can be hydrogen and R¹² and R¹⁶ can be non-hydrogensubstituents, R¹², R¹⁴, and R¹⁶ can be hydrogen and R¹³ and R¹⁵ can benon-hydrogen substituents, or R¹³ and R¹⁵ can be hydrogen and R¹², R¹⁴,and R¹⁶ can be non-hydrogen substituents. In some embodiments wherein R¹has Structure G2, R¹³, R¹⁴, R¹⁵, and R¹⁶ can be hydrogen and R¹² can bea non-hydrogen substituent, R¹², R¹³, R¹⁵, and R¹⁶ can be hydrogen andR¹⁴ can be a non-hydrogen substituent, R¹³, R¹⁵, and R¹⁶ can be hydrogenand R¹² and R¹⁴ can be non-hydrogen substituents, R¹³, R¹⁴, and R¹⁵ canbe hydrogen and R¹² and R¹⁶ can be non-hydrogen substituents, or R¹³ andR¹⁵ can be hydrogen and R¹², R¹⁴, and R¹⁶ can be non-hydrogensubstituents; alternatively, R¹³, R¹⁴, R¹⁵, and R¹⁶ can be hydrogen andR¹² can be a non-hydrogen substituent, R¹², R¹³, R¹⁵, and R¹⁶ can behydrogen and R¹⁴ can be a non-hydrogen substituent, R¹³, R¹⁵, and R¹⁶can be hydrogen and R¹² and R¹⁴ can be non-hydrogen substituents, orR¹³, R¹⁴, and R¹⁵ can be hydrogen and R¹² and R¹⁶ can be non-hydrogensubstituents; alternatively, R¹², R¹⁴, R¹⁵, and R¹⁶ can be hydrogen andR¹³ can be a non-hydrogen substituent, or R¹², R¹⁴, and R¹⁶ can behydrogen and R¹³ and R¹⁵ can be non-hydrogen substituents;alternatively, R¹³, R¹⁴, R¹⁵, and R¹⁶ can be hydrogen and R¹² can be anon-hydrogen substituent, or R¹², R¹³, R¹⁵, and R¹⁶ can be hydrogen andR¹⁴ can be a non-hydrogen substituent; alternatively, R¹³, R¹⁵, and R¹⁶can be hydrogen and R¹² and R¹⁴ can be non-hydrogen substituents, R¹³,R¹⁴, and R¹⁵ can be hydrogen and R¹² and R¹⁶ can be non-hydrogensubstituents, or R¹³ and R¹⁵ can be hydrogen and R¹², R¹⁴, and R¹⁶ canbe non-hydrogen substituents; or alternatively, R¹³, R¹⁵, and R¹⁶ can behydrogen and R¹² and R¹⁴ can be non-hydrogen substituents, or R¹³, R¹⁴,and R¹⁵ can be hydrogen and R¹² and R¹⁶ can be non-hydrogensubstituents. In other embodiments wherein R¹ has Structure G2, R¹²,R¹³, R¹⁴, R¹⁵, and R¹⁶ can be hydrogen; alternatively, R¹³, R¹⁴, R¹⁵,and R¹⁶ can be hydrogen and R¹² can be a non-hydrogen substituent;alternatively, R¹², R¹⁴, R¹⁵, and R¹⁶ can be hydrogen and R¹³ can be anon-hydrogen substituent; alternatively, R¹², R¹³, R¹⁵, and R¹⁶ can behydrogen and R¹⁴ can be a non-hydrogen substituent; alternatively, R¹³,R¹⁵, and R¹⁶ can be hydrogen and R¹² and R¹⁴ can be non-hydrogensubstituents; alternatively, R¹³, R¹⁴, and R¹⁵ can be hydrogen and R¹²and R¹⁶ can be non-hydrogen substituents; alternatively, R¹², R¹⁴, andR¹⁶ can be hydrogen and R¹³ and R¹⁵ and can be non-hydrogensubstituents; or alternatively, R¹³ and R¹⁵ can be hydrogen and R¹²,R¹⁴, and R¹⁶ can be non-hydrogen substituents. Substituents (general andspecific) are independently disclosed herein and can be utilized withoutlimitation as R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ for the R¹ group havingStructure G2.

In an embodiment, when the N¹ nitrogen atom of the N²-phosphinylformamidine group is attached to a carbon atom of a cycloalkane or arenering or ring system, the cyclic R¹ group can comprise at least onesubstituent located on a carbon atom adjacent to the carbon atomattached to N¹ nitrogen atom of the N²-phosphinyl formamidine group. Insome embodiments, when the N¹ nitrogen atom of the N²-phosphinylformamidine group is attached to a carbon atom of a cycloalkane or arenering or ring system, the cyclic R¹ group can comprise at least onesubstituent located on each carbon atom adjacent to the carbon atomattached to N¹ nitrogen atom of the N²-phosphinyl formamidine group. Inanother embodiment, when the N¹ nitrogen atom of the N²-phosphinylformamidine group is attached to a carbon atom of a cycloalkane or arenering or ring system, the cyclic R¹ group can consist of one substituentlocated on each carbon atom adjacent to the carbon atom attached to N¹nitrogen atom of the N²-phosphinyl formamidine group. In otherembodiments, when the N¹ nitrogen atom of the N²-phosphinyl formamidinegroup is attached to a carbon atom of a cycloalkane or arene ring orring system, the cyclic R¹ group can comprise only one substituentlocated on a carbon atom adjacent to the carbon atom attached to N¹nitrogen atom of the N²-phosphinyl formamidine group. In anotherembodiment, when the N¹ nitrogen atom of the N²-phosphinyl formamidinegroup is attached to a carbon atom of a cycloalkane or arene ring orring system, the cyclic R¹ group can comprise only one substituentlocated on each carbon atom adjacent to the carbon atom attached to N¹nitrogen atom of the N²-phosphinyl formamidine group. In yet anotherembodiment, when the N¹ nitrogen atom of the N²-phosphinyl formamidinegroup is attached to a carbon atom of a cycloalkane or arene ring orring system, the cyclic R¹ group can consist of only one substituentlocated on each carbon atom adjacent to the carbon atom attached to N¹nitrogen atom of the N²-phosphinyl formamidine group.

In a non-limiting embodiment, R¹ can be a phenyl group, a 2-alkylphenylgroup, a 3-alkylphenyl group, a 4-alkylphenyl group, a 2,4-dialkylphenylgroup, a 2,6-dialkylphenyl group, a 3,5-dialkylphenyl group, or a2,4,6-trialkylphenyl group; alternatively, a 2-alkylphenyl group, a4-alkylphenyl group, a 2,4-dialkylphenyl group, a 2,6-dialkylphenylgroup, or a 2,4,6-trialkylphenyl group; alternatively, a 2-alkylphenylgroup or a 4-alkylphenyl group; alternatively, a 2,4-dialkylphenylgroup, a 2,6-dialkylphenyl group, or a 2,4,6-trialkylphenyl group;alternatively, a 2,4-dialkylphenyl group or a 2,6-dialkylphenyl group;alternatively, a 2,6-dialkylphenyl group, or a 2,4,6-trialkylphenylgroup; alternatively, a 3-alkylphenyl group or a 3,5-dialkylphenylgroup; alternatively, a 2-alkylphenyl group or a 2,6-dialkylphenylgroup; alternatively, a 2-alkylphenyl group; alternatively, a3-alkylphenyl group; alternatively, a 4-alkylphenyl group;alternatively, a 2,4-dialkylphenyl group; alternatively, a2,6-dialkylphenyl group; alternatively, a 3,5-dialkylphenyl group; oralternatively, a 2,4,6-trialkylphenyl group. In another non-limitingembodiment, R¹ can be a napht-1-yl group, a naphth-2-yl group, a2-alkylnaphth-1-yl group, a 1-alkylnaphth-2-yl group, a3-alkylnapth-2-yl group, or a 1,3-dialkylnaphth-2-yl group;alternatively, a napht-1-yl group or a 2-alkylnaphth-1-yl group;alternatively, a naphth-2-yl group, a 1-alkylnaphth-2-yl group, a3-alkylnapth-2-yl group, or a 1,3-dialkylnaphth-2-yl group;alternatively, a napht-1-yl group; alternatively, a naphth-2-yl group;alternatively, a 2-alkylnaphth-1-yl group; alternatively, a1-alkylnaphth-2-yl group; alternatively, a 3-alkylnapth-2-yl group; oralternatively, a 1,3-dialkylnaphth-2-yl group. In other non-limitingembodiments, R¹ can be a cyclohexyl group, a 2-alkylcyclohexyl group, ora 2,6-dialkylcyclohexyl group; alternatively, a cyclopentyl group, a2-alkylcyclopentyl group, or a 2,5-dialkylcyclopentyl group;alternatively, a cyclohexyl group; alternatively, a 2-alkylcyclohexylgroup; alternatively, a 2,6-dialkylcyclohexyl group; alternatively, acyclopentyl group; alternatively, a 2-alkylcyclopentyl group; oralternatively, a 2,5-dialkylcyclopentyl group. Alkyl group substituents(general and specific) are independently described herein and can beutilized, without limitation, to further describe the alkylphenyl,dialkylphenyl, trialkylphenyl, naphthyl, dialkylnaphthyl,alkylcyclohexyl, dialkylcyclohexyl, alkylcyclopentyl, ordialkylcyclopentyl groups that can be utilized R¹. Generally, the alkylsubstituents of a dialkyl or trialkyl phenyl, naphthyl, cyclohexyl, orcyclopentyl group can be the same; or alternatively, the alkylsubstituents of a dialkyl or trialkyl phenyl, naphthyl, cyclohexyl, orcyclopentyl group can be different.

In another non-limiting embodiment, R¹ can be a phenyl group, a2-alkoxyphenyl group, a 3-alkoxyphenyl group, a 4-alkoxyphenyl group, ora 3,5-dialkoxyphenyl group; alternatively, a 2-alkoxyphenyl group or a4-alkoxyphenyl group; alternatively, a 3-alkoxyphenyl group or a3,5-dialkoxyphenyl group; alternatively, a 2-alkoxyphenyl group;alternatively, a 3-alkoxyphenyl group; alternatively, a 4-alkoxyphenylgroup; alternatively, a 3,5-dialkoxyphenyl group. Alkoxy groupsubstituents (general and specific) are independently described hereinand can be utilized, without limitation, to further describe thealkoxyphenyl or dialkoxyphenyl groups that can be utilized R¹.Generally, the alkoxy substituents of a dialkoxyphenyl group can be thesame; or alternatively, the alkoxy substituents of a dialkoxyphenylgroup can be different.

In other non-limiting embodiments, R¹ can be a phenyl group, a2-halophenyl group, a 3-halophenyl group, a 4-halophenyl group, a2,6-dihalophenyl group, or a 3,5-dialkylphenyl group; alternatively, a2-halophenyl group, a 4-halophenyl group, or a 2,6-dihalophenyl group;alternatively, a 2-halophenyl group or a 4-halophenyl group;alternatively, a 3-halophenyl group or a 3,5-dihalophenyl group;alternatively, a 2-halophenyl group; alternatively, a 3-halophenylgroup; alternatively, a 4-halophenyl group; alternatively, a2,6-dihalophenyl group; or alternatively, a 3,5-dihalophenyl group.Halides are independently described herein and can be utilized, withoutlimitation, to further describe the halophenyl or dihalophenyl groupsthat can be utilized as R¹. Generally, the halides of a dihalophenylgroup can be the same; or alternatively, the halides of a dihalophenylgroup can be different.

In a non-limiting embodiment, R¹ can be a 2-methylphenyl group, a2-ethylphenyl group, a 2-n-propylphenyl group, a 2-isopropylphenylgroup, a 2-tert-butylphenyl group, a 3-methylphenyl group, a2,6-dimethylphenyl group, a 2,6-diethylphenyl group, a2,6-di-n-propylphenyl group, a 2,6-diisopropylphenyl group, a2,6-di-tert-butylphenyl group, a 2-isopropyl-6-methylphenyl group, a3,5-dimethyl group, or a 2,4,6-trimethylphenyl group; alternatively, a2-methylphenyl group, a 2-ethylphenyl group, a 2-n-propylphenyl group, a2-isopropylphenyl group, or a 2-tert-butylphenyl group; alternatively, a2,6-dimethylphenyl group, a 2,6-diethylphenyl group, a2,6-di-n-propylphenyl group, a 2,6-diisopropylphenyl group, a2,6-di-tert-butylphenyl group, or a 2-isopropyl-6-methylphenyl group;alternatively, a 2-methylphenyl group; alternatively, a 2-ethylphenylgroup; alternatively, a 2-n-propylphenyl group; alternatively, a2-isopropylphenyl group; alternatively, a 2-tert-butylphenyl group;alternatively, a 3-methylphenyl group; alternatively, a2,6-dimethylphenyl group; alternatively, a 2,6-diethylphenyl group;alternatively, a 2,6-di-n-propylphenyl group; alternatively, a2,6-diisopropylphenyl group; alternatively, a 2,6-di-tert-butylphenylgroup; alternatively, a 2-isopropyl-6-methylphenyl group; alternatively,a 3,5-dimethylphenyl group; or alternatively, a 2,4,6-trimethylphenylgroup. In another non-limiting embodiment, R¹ can be a2-methylcyclohexyl group, a 2-ethylcyclohexyl group, a2-isopropylcyclohexyl group, a 2-tert-butylcyclohexyl group, a2,6-dimethylcyclohexyl group, a 2,6-diethylcyclohexyl group, a2,6-diisopropylcyclohexyl group, or a 2,6-di-tert-butylcyclohexyl group;alternatively, a 2-methylcyclohexyl group, a 2-ethylcyclohexyl group, a2-isopropylcyclohexyl group, or a 2-tert-butylcyclohexyl group;alternatively, a 2,6-dimethylcyclohexyl group, a 2,6-diethylcyclohexylgroup, a 2,6-diisopropylcyclohexyl group, or a2,6-di-tert-butylcyclohexyl group; alternatively, a 2-methylcyclohexylgroup; alternatively, a 2-ethylcyclohexyl group; alternatively, a2-isopropylcyclohexyl group; alternatively, a 2-tert-butylcyclohexylgroup; alternatively, a 2,6-dimethylcyclohexyl group; alternatively, a2,6-diethylcyclohexyl group; alternatively, a 2,6-diisopropylcyclohexylgroup; or alternatively, a 2,6-di-tert-butylcyclohexyl group. In anothernon-limiting embodiment, R¹ can be a 2-methylnaphth-1-yl group, a2-ethylnaphth-1-yl group, a 2-n-propylnaphth-1-yl group, a2-isopropylnaphth-1-yl group, or a 2-tert-butylnaphth-1-yl group;alternatively, a 2-methylnaphth-1-yl group; alternatively, a2-ethylnaphth-1-yl group; alternatively, a 2-n-propylnaphth-1-yl group;alternatively, a 2-isopropylnaphth-1-yl group; or alternatively, a2-tert-butylnaphth-1-yl group.

In a non-limiting embodiment, R¹ can be a 3-methoxyphenyl group, a3-ethoxyphenyl group, a 3-isopropoxyphenyl group, a 3-tert-butoxyphenylgroup, a 4-methoxyphenyl group, a 4-ethoxyphenyl group, a4-isopropoxyphenyl group, a 4-tert-butoxyphenyl group, a3,5-dimethoxyphenyl group, a 3,5-diethoxyphenyl group, a3,5-diisopropoxyphenyl group, or a 3,5-di-tert-butoxyphenyl group;alternatively, a 3-methoxyphenyl group, a 3-ethoxyphenyl group, a3-isopropoxyphenyl group, or a 3-tert-butoxyphenyl group; alternatively,a 4-methoxyphenyl group, a 4-ethoxyphenyl group, a 4-isopropoxy-phenylgroup, or a 4-tert-butoxyphenyl group; or alternatively, a3,5-dimethoxyphenyl group, a 3,5-diethoxyphenyl group, a3,5-diisopropoxyphenyl group, or a 3,5-di-tert-butoxyphenyl group. Inother non-limiting embodiments, R¹ can be a 3-methoxyphenyl group;alternatively, a 3-ethoxyphenyl group; alternatively, a3-isopropoxyphenyl group; alternatively, a 3-tert-butoxyphenyl group;alternatively, a 4-methoxyphenyl group; alternatively, a 4-ethoxyphenylgroup; alternatively, a 4-isopropoxyphenyl group; alternatively, a4-tert-butoxyphenyl group; alternatively, a 3,5-dimethoxyphenyl group;alternatively, a 3,5-diethoxyphenyl group; alternatively, a3,5-diisopropoxyphenyl group; or alternatively, a3,5-di-tert-butoxyphenyl group.

In an aspect, R³ can be hydrogen. In another aspect, R³ can be anorganyl group; alternatively, an organyl group consisting essentially ofinert functional groups; or alternatively, a hydrocarbyl group. In anembodiment, R³ can be a C₁ to C₃₀ organyl group; alternatively, a C₁ toC₂₀ organyl group; alternatively, a C₁ to C₁₅ organyl group;alternatively, a C₁ to C₁₀ organyl group; or alternatively, a C₁ to C₅organyl group. In an embodiment, R³ can be a C₁ to C₃₀ organyl groupconsisting essentially of inert functional groups; alternatively, a C₁to C₂₀ organyl group consisting essentially of inert functional groups;alternatively, a C₁ to C₁₅ organyl group consisting essentially of inertfunctional groups; alternatively, a C₁ to C₁₀ organyl group consistingessentially of inert functional groups; or alternatively, a C₁ to C₅organyl group consisting essentially of inert functional groups. In anembodiment, R³ can be a C₁ to C₃₀ hydrocarbyl group; alternatively, a C₁to C₂₀ hydrocarbyl group; alternatively, a C₁ to C₁₅ hydrocarbyl group;alternatively, a C₁ to C₁₀ hydrocarbyl group; or alternatively, a C₁ toC₅ hydrocarbyl group. In yet other embodiments, R³ can be a C₃ to C₃₀aromatic group; alternatively, a C₃ to C₂₀ aromatic group;alternatively, a C₃ to C₁₅ aromatic group; or alternatively, a C₃ to C₁₀aromatic group.

In an aspect, R³ can be a C₁ to C₃₀ alkyl group, a C₄ to C₃₀ cycloalkylgroup, a C₄ to C₃₀ substituted cycloalkyl group, a C₆ to C₃₀ aryl group,or a C₆ to C₃₀ substituted aryl group; alternatively, a C₄ to C₃₀cycloalkyl group or a C₄ to C₃₀ substituted cycloalkyl group;alternatively, a C₆ to C₃₀ aryl group or a C₆ to C₃₀ substituted arylgroup; alternatively, a C₁ to C₃₀ alkyl group; alternatively, a C₄ toC₃₀ cycloalkyl group; alternatively, a C₄ to C₃₀ substituted cycloalkylgroup; alternatively, a C₆ to C₃₀ aryl group; or alternatively, a C₆ toC₃₀ substituted aryl group. In an embodiment, R³ can be a C₁ to C₁₅alkyl group, a C₄ to C₂₀ cycloalkyl group, a C₄ to C₂₀ substitutedcycloalkyl group, a C₆ to C₂₀ aryl group, or a C₆ to C₂₀ substitutedaryl group; alternatively, a C₄ to C₂₀ cycloalkyl group or a C₄ to C₂₀substituted cycloalkyl group; alternatively, a C₆ to C₂₀ aryl group or aC₆ to C₂₀ substituted aryl group; alternatively, a C₁ to C₁₅ alkylgroup; alternatively, a C₄ to C₂₀ cycloalkyl group; alternatively, a C₄to C₂₀ substituted cycloalkyl group; alternatively, a C₆ to C₂₀ arylgroup; or alternatively, a C₆ to C₂₀ substituted aryl group. In otherembodiments, R³ can be a C₁ to C₁₀ alkyl group, a C₄ to C₁₅ cycloalkylgroup, a C₄ to C₁₅ substituted cycloalkyl group, a C₆ to C₁₅ aryl group,or a C₆ to C₁₅ substituted aryl group; alternatively, a C₄ to C₁₅cycloalkyl group or a C₄ to C₁₅ substituted cycloalkyl group;alternatively, a C₆ to C₁₅ aryl group or a C₆ to C₁₅ substituted arylgroup; alternatively, a C₁ to C₁₀ alkyl group; alternatively, a C₄ toC₁₅ cycloalkyl group; alternatively, a C₄ to C₁₅ substituted cycloalkylgroup; alternatively, a C₆ to C₁₅ aryl group; or alternatively, a C₆ toC₁₅ substituted aryl group. In further embodiments, R³ can be a C₁ to C₅alkyl group. Substituents (general and specific) are independentlydisclosed herein and can be utilized without limitation to furtherdescribe substituted groups which can be utilized as R³.

In an embodiment, R³ can be a methyl group, an ethyl group, a propylgroup, a butyl group, a pentyl group, a hexyl group, a heptyl group, anoctyl group, a nonyl group, or a decyl group. In some embodiments, R³can be a methyl group, an ethyl group, an n-propyl group, an iso-propylgroup, an n-butyl group, an iso-butyl group, a sec-butyl group, atert-butyl group, an n-pentyl group, an iso-pentyl group, a sec-pentylgroup, or a neopentyl group; alternatively, a methyl group, an ethylgroup, an iso-propyl group, a tert-butyl group, or a neopentyl group;alternatively, a methyl group; alternatively, an ethyl group;alternatively, an n-propyl group; alternatively, an iso-propyl group;alternatively, a tert-butyl group; or alternatively, a neopentyl group.In some embodiments, the alkyl groups which can be utilized as R³ can besubstituted. Each substituent of a substituted alkyl group independentlycan be a halogen or a hydrocarboxy group; alternatively, a halogen; oralternatively, a hydrocarboxy group. Halogens and hydrocarboxy groups(general and specific) are independently disclosed herein (e.g., asgeneral substituents and substituents for substituted R¹ groups) and canbe utilized without limitation to further describe the substituted alkylgroup which can be utilized as R³.

In an embodiment, R³ can be a cyclobutyl group, a substituted cyclobutylgroup, a cyclopentyl group, a substituted cyclopentyl group, acyclohexyl group, a substituted cyclohexyl group, a cycloheptyl group, asubstituted cycloheptyl group, a cyclooctyl group, or a substitutedcyclooctyl group. In some embodiments, R³ can be a cyclopentyl group, asubstituted cyclopentyl group, a cyclohexyl group, or a substitutedcyclohexyl group. In other embodiments, R³ can be a cyclopentyl group ora substituted cyclopentyl group; or alternatively, a cyclohexyl group ora substituted cyclohexyl group. In further embodiments, R³ can be acyclopentyl group; alternatively, a substituted cyclopentyl group; acyclohexyl group; or alternatively, a substituted cyclohexyl group.Substituents (general and specific) are independently disclosed hereinand can be utilized without limitation to further describe thesubstituted cycloalkyl group which can be utilized as R³.

In an aspect, R³ can have Structure G5:

wherein, the undesignated valency is attached to the N² nitrogen atom ofthe N²-phosphinyl formamidine group. Generally, R^(31c), R^(32c),R^(33c), R^(34c), and R^(35c) independently can be hydrogen or anon-hydrogen substituent, and n can be an integer from 1 to 5. In anembodiment wherein R³ has Structure G5, R^(31c), R^(33c), R^(34c), andR^(35c) can be hydrogen and R^(32c) can be any non-hydrogen substituentdisclosed herein; or alternatively, R^(31c), R^(33c), and R^(35c) can behydrogen and R^(32c) and R^(34c) independently can be any non-hydrogensubstituent disclosed herein. In an embodiment, n can be an integer from1 to 4; or alternatively, from 2 to 4. In other embodiments, n can be 2or 3; alternatively, 2; or alternatively 3. Substituents (general andspecific) are independently disclosed herein and can be utilized withoutlimitation to further describe a non-hydrogen substituent which can beutilized without limitation as R^(31c), R^(32c), R^(33c), R^(34c),and/or R^(35c) for the R³ group having Structure G5.

In an embodiment, R³ can be a phenyl group or a substituted phenylgroup. In some embodiments, R³ can be a phenyl group; or alternatively,a substituted phenyl group. In an embodiment, the R³ substituted phenylgroup can be a 2-substituted phenyl group, a 3-substituted phenyl group,a 4-substituted phenyl group, a 2,4-disubstituted phenyl group, a2,6-disubstituted phenyl group, a 3,5-disubstituted phenyl group, or a2,4,6-trisubstituted phenyl group. In other embodiments, the R³substituted phenyl group can be a 2-substituted phenyl group, a4-substituted phenyl group, a 2,4-disubstituted phenyl group, a2,6-disubstituted phenyl group, or a 2,4,6-trisubstituted phenyl group;alternatively, a 2-substituted phenyl group, a 4-substituted phenylgroup, a 2,4-disubstituted phenyl group, or a 2,6-disubstituted phenylgroup; alternatively, a 3-substituted phenyl group or a3,5-disubstituted phenyl group; alternatively, a 2-substituted phenylgroup or a 4-substituted phenyl group; alternatively, a2,4-disubstituted phenyl group, a 2,6-disubstituted phenyl group, or a2,4,6-trisubstituted phenyl group; alternatively, a 2,6-disubstitutedphenyl group or a 2,4,6-trisubstituted phenyl group; alternatively, a2,4-disubstituted phenyl group or a 2,6-disubstituted phenyl group;alternatively, a 2-substituted phenyl group; alternatively, a3-substituted phenyl group; alternatively, a 4-substituted phenyl group;alternatively, a 2,4-disubstituted phenyl group; alternatively, a2,6-disubstituted phenyl group; alternatively, a 3,5-disubstitutedphenyl group; or alternatively, a 2,4,6-trisubstituted phenyl group.Substituents (general and specific) are independently disclosed hereinand can be utilized without limitation to further describe anysubstituted phenyl group which can be utilized as R³.

In an aspect, R³ can have Structure G6:

wherein the undesignated valency is attached to the N¹ nitrogen atom ofthe N²-phosphinyl formamidine group. Generally, R³², R³³, R³⁴, R³⁵, andR³⁶ independently can be hydrogen or a non-hydrogen substituent. In anembodiment wherein R³ has Structure G6, R³², R³³, R³⁴, R³⁵, and R³⁶ canbe hydrogen, R³³, R³⁴, R³⁵, and R³⁶ can be hydrogen and R³² can be anon-hydrogen substituent, R³², R³⁴, R³⁵, and R³⁶ can be hydrogen and R³³can be a non-hydrogen substituent, R³², R³³, R³⁵, and R³⁶ can behydrogen and R³⁴ can be a non-hydrogen substituent, R³³, R³⁵, and R³⁶can be hydrogen and R³² and R³⁴ can be non-hydrogen substituents, R³³,R³⁴, and R³⁵ can be hydrogen and R³² and R³⁶ can be non-hydrogensubstituents, R³², R³⁴, and R³⁶ can be hydrogen and R³³ and R³⁵ can benon-hydrogen substituents, or R³³ and R³⁵ can be hydrogen and R³², R³⁴,and R³⁶ can be non-hydrogen substituents. In some embodiments wherein R³has Structure G6, R³³, R³⁴, R³⁵, and R³⁶ can be hydrogen and R³² can bea non-hydrogen substituent, R³², R³³, R³⁵, and R³⁶ can be hydrogen andR³⁴ can be a non-hydrogen substituent, R³³, R³⁵, and R³⁶ can be hydrogenand R³² and R³⁴ can be non-hydrogen substituents, R³³, R³⁴, and R³⁵ canbe hydrogen and R³² and R³⁶ can be non-hydrogen substituents, or R³³ andR³⁵ can be hydrogen and R³², R³⁴, and R³⁶ can be non-hydrogensubstituents; alternatively, R³³, R³⁴, R³⁵, and R³⁶ can be hydrogen andR³² can be a non-hydrogen substituent, R³², R³³, R³⁵, and R³⁶ can behydrogen and R³⁴ can be a non-hydrogen substituent, R³³, R³⁵, and R³⁶can be hydrogen and R³² and R³⁴ can be non-hydrogen substituents, orR³³, R³⁴, and R³⁵ can be hydrogen and R³² and R³⁶ can be non-hydrogensubstituents; alternatively, R³², R³⁴, R³⁵, and R³⁶ can be hydrogen andR³³ can be a non-hydrogen substituent, or R³², R³⁴, and R³⁶ can behydrogen and R³³ and R³⁵ can be non-hydrogen substituents;alternatively, R³³, R³⁴, R³⁵, and R³⁶ can be hydrogen and R³² can be anon-hydrogen substituent, or R³², R³³, R³⁵, and R³⁶ can be hydrogen andR³⁴ can be a non-hydrogen substituent; alternatively, R³³, R³⁵, and R³⁶can be hydrogen and R³² and R³⁴ can be non-hydrogen substituents, R³³,R³⁴, and R³⁵ can be hydrogen and R³² and R³⁶ can be non-hydrogensubstituents, or R³³ and R³⁵ can be hydrogen and R³², R³⁴, and R³⁶ canbe non-hydrogen substituents; or alternatively, R³³, R³⁵, and R³⁶ can behydrogen and R³² and R³⁴ can be non-hydrogen substituents, or R³³, R³⁴,and R³⁵ can be hydrogen and R³² and R³⁶ can be non-hydrogensubstituents. In other embodiments wherein R³ has Structure G6, R³²,R³³, R³⁴, R³⁵, and R³⁶ can be hydrogen; alternatively, R³³, R³⁴, R³⁵,and R³⁶ can be hydrogen and R³² can be a non-hydrogen substituent;alternatively, R³², R³⁴, R³⁵, and R³⁶ can be hydrogen and R³³ can be anon-hydrogen substituent; alternatively, R³², R³³, R³⁵, and R³⁶ can behydrogen and R³⁴ can be a non-hydrogen substituent; alternatively, R³³,R³⁵, and R³⁶ can be hydrogen and R³² and R³⁴ can be non-hydrogensubstituents; alternatively, R³³, R³⁴, and R³⁵ can be hydrogen and R³²and R³⁶ can be non-hydrogen substituents; alternatively, R³², R³⁴, andR³⁶ can be hydrogen and R³³ and R³⁵ and can be non-hydrogensubstituents; or alternatively, R³³ and R³⁵ can be hydrogen and R³²,R³⁴, and R³⁶ can be non-hydrogen substituents. Substituents (general andspecific) are independently disclosed herein and can be utilized withoutlimitation as R³², R³³, R³⁴, R³⁵, and R³⁶ for the R³ group havingStructure G6.

In a non-limiting embodiment, R³ can be a phenyl group, a 2-alkylphenylgroup, a 3-alkylphenyl group, a 4-alkylphenyl group, a 2,4-dialkylphenylgroup, a 2,6-dialkylphenyl group, a 3,5-dialkylphenyl group, or a2,4,6-trialkylphenyl group; alternatively, a 2-alkylphenyl group, a4-alkylphenyl group, a 2,4-dialkylphenyl group, a 2,6-dialkylphenylgroup, or a 2,4,6-trialkylphenyl group; alternatively, a 2-alkylphenylgroup or a 4-alkylphenyl group; alternatively, a 2,4-dialkylphenylgroup, a 2,6-dialkylphenyl group, or a 2,4,6-trialkylphenyl group;alternatively, a 2,4-dialkylphenyl group or a 2,6-dialkylphenyl group;alternatively, a 2,6-dialkylphenyl group, or a 2,4,6-trialkylphenylgroup; alternatively, a 3-alkylphenyl group or a 3,5-dialkylphenylgroup; alternatively, a 2-alkylphenyl group or a 2,6-dialkylphenylgroup; alternatively, a 2-alkylphenyl group; alternatively, a3-alkylphenyl group; alternatively, a 4-alkylphenyl group;alternatively, a 2,4-dialkylphenyl group; alternatively, a2,6-dialkylphenyl group; alternatively, a 3,5-dialkylphenyl group; oralternatively, a 2,4,6-trialkylphenyl group. In another non-limitingembodiment, R³ can be a phenyl group, a 2-alkoxyphenyl group, a3-alkoxyphenyl group, a 4-alkoxyphenyl group, or a 3,5-dialkoxyphenylgroup; alternatively, a 2-alkoxyphenyl group or a 4-alkoxyphenyl group;alternatively, a 3-alkoxyphenyl group or 3,5-dialkoxyphenyl group;alternatively, a 2-alkoxyphenyl group; alternatively, a 3-alkoxyphenylgroup; alternatively, a 4-alkoxyphenyl group; alternatively, a3,5-dialkoxyphenyl group. In other non-limiting embodiments, R¹ can be aphenyl group, a 2-halophenyl group, a 3-halophenyl group, a 4-halophenylgroup, a 2,6-dihalophenyl group, or a 3,5-dialkylphenyl group;alternatively, a 2-halophenyl group, a 4-halophenyl group, or a2,6-dihalophenyl group; alternatively, a 2-halophenyl group or a4-halophenyl group; alternatively, a 3-halophenyl group or a3,5-dihalophenyl group; alternatively, a 2-halophenyl group;alternatively, a 3-halophenyl group; alternatively, a 4-halophenylgroup; alternatively, a 2,6-dihalophenyl group; or alternatively, a3,5-dihalophenyl group. Halides, alkyl group substituents (general andspecific), and alkoxy group substituents (general and specific) areindependently described herein and can be utilized, without limitation,to further describe the alkylphenyl, dialkylphenyl, trialkylphenyl,alkoxyphenyl, dialkoxyphenyl, halophenyl, or dihalophenyl groups thatcan be utilized as R³. Generally, the halides, alkyl substituents, oralkoxy substituents of a dialkyl, trialkyl phenyl, dialkoxyphenyl, ordihalophenyl group can be the same; or alternatively the halo, alkylsubstituents, or alkoxy substituents of alkylphenyl, dialkylphenyl,trialkylphenyl, dialkoxyphenyl, or dihalophenyl groups can be different.

In a non-limiting embodiment, R³ can be a 2-methylphenyl group, a2-ethylphenyl group, a 2-isopropylphenyl group, a 2-tert-butylphenylgroup, a 4-methylphenyl group, a 4-ethylphenyl group, a4-isopropylphenyl group, a 4-tert-butylphenyl group, a2,6-dimethylphenyl group, a 2,6-diethylphenyl group, a2,6-diisopropylphenyl group, or a 2,6-di-tert-butylphenyl group;alternatively, a 2-methylphenyl group, a 2-ethylphenyl group, a2-isopropylphenyl group, or a 2-tert-butylphenyl group, a 4-methylphenylgroup, a 4-ethylphenyl group, a 4-isopropylphenyl group, or a4-tert-butylphenyl group; alternatively, a 2-methylphenyl group, a2-ethylphenyl group, a 2-isopropylphenyl group, or a 2-tert-butylphenylgroup; alternatively, a 4-methylphenyl group, a 4-ethylphenyl group, a4-isopropylphenyl group, or a 4-tert-butylphenyl group; oralternatively, a 2,6-dimethylphenyl group, a 2,6-diethylphenyl group, a2,6-di-n-propylphenyl group, a 2,6-diisopropylphenyl group, or a2,6-di-tert-butylphenyl group. In another non-limiting embodiment, R³can be a 2-methylphenyl group; alternatively, a 2-ethylphenyl group;alternatively, a 2-isopropylphenyl group; alternatively, a2-tert-butylphenyl group; alternatively, a 4-methylphenyl group;alternatively, a 4-ethylphenyl group; alternatively, a 4-isopropylphenylgroup; or alternatively, a 4-tert-butylphenyl group.

In an aspect, R⁴ and/or R⁵ independently can be an organyl group;alternatively, an organyl group consisting essentially of inertfunctional groups; or alternatively, a hydrocarbyl group. In anembodiment, R⁴ and/or R⁵ independently can be a C₁ to C₃₀ organyl group;alternatively, a C₁ to C₂₀ organyl group; alternatively, a C₁ to C₁₅organyl group; alternatively, a C₁ to C₁₀ organyl group; oralternatively, a C₁ to C₅ organyl group. In an embodiment, R⁴ and/or R⁵independently can be a C₁ to C₃₀ organyl group consisting essentially ofinert functional groups; alternatively, a C₁ to C₂₀ organyl groupconsisting essentially of inert functional groups; alternatively, a C₁to C₁₅ organyl group consisting essentially of inert functional groups;alternatively, a C₁ to C₁₀ organyl group consisting essentially of inertfunctional groups; or alternatively, a C₁ to C₅ organyl group consistingessentially of inert functional groups. In an embodiment, R⁴ and/or R⁵independently can be a C₁ to C₃₀ hydrocarbyl group; alternatively, a C₁to C₂₀ hydrocarbyl group; alternatively, a C₁ to C₁₅ hydrocarbyl group;alternatively, a C₁ to C₁₀ hydrocarbyl group; or alternatively, a C₁ toC₅ hydrocarbyl group. In yet other embodiments, R⁴ and R⁵ can beindependently selected from a C₃ to C₃₀ aromatic group; alternatively, aC₃ to C₂₀ aromatic group; alternatively, a C₃ to C₁₅ aromatic group; oralternatively, a C₃ to C₁₀ aromatic group. In an aspect, R⁴ and R⁵ canbe joined to form a ring (regardless of particular type ofgroup—organyl, organyl consisting of inert functional groups,hydrocarbyl, or any species within) containing the phosphorus atom ofthe N²-phosphinyl formamidine group.

In another aspect, R⁴ and/or R⁵ independently can be a C₁ to C₃₀ alkylgroup, a C₄ to C₃₀ cycloalkyl group, a C₄ to C₃₀ substituted cycloalkylgroup, a C₆ to C₃₀ aryl group, or a C₆ to C₃₀ substituted aryl group;alternatively, a C₄ to C₃₀ cycloalkyl group or a C₄ to C₃₀ substitutedcycloalkyl group; alternatively, a C₆ to C₃₀ aryl group or a C₆ to C₃₀substituted aryl group; alternatively, a C₁ to C₃₀ alkyl group;alternatively, a C₄ to C₃₀ cycloalkyl group; alternatively, a C₄ to C₃₀substituted cycloalkyl group; alternatively, a C₆ to C₃₀ aryl group; oralternatively, a C₆ to C₃₀ substituted aryl group. In an embodiment, R⁴and R⁵ independently can be a C₁ to C₁₅ alkyl group, a C₄ to C₂₀cycloalkyl group, a C₄ to C₂₀ substituted cycloalkyl group, a C₆ to C₂₀aryl group, or a C₆ to C₂₀ substituted aryl group; alternatively, a C₄to C₂₀ cycloalkyl group or a C₄ to C₂₀ substituted cycloalkyl group;alternatively, a C₆ to C₂₀ aryl group or a C₆ to C₂₀ substituted arylgroup; alternatively, a C₁ to C₁₅ alkyl group; alternatively, a C₄ toC₂₀ cycloalkyl group; alternatively, a C₄ to C₂₀ substituted cycloalkylgroup; alternatively, a C₆ to C₂₀ aryl group; or alternatively, a C₆ toC₂₀ substituted aryl group. In other embodiments, R⁴ and R⁵independently can be a C₁ to C₁₀ alkyl group, a C₄ to C₁₅ cycloalkylgroup, a C₄ to C₁₅ substituted cycloalkyl group, a C₆ to C₁₅ aryl group,or a C₆ to C₁₅ substituted aryl group; alternatively, a C₄ to C₁₅cycloalkyl group or a C₄ to C₁₅ substituted cycloalkyl group;alternatively, a C₆ to C₁₅ aryl group or a C₆ to C₁₅ substituted arylgroup; alternatively, a C₁ to C₁₀ alkyl group; alternatively, a C₄ toC₁₅ cycloalkyl group; alternatively, a C₄ to C₁₅ substituted cycloalkylgroup; alternatively, a C₆ to C₁₅ aryl group; or alternatively, a C₆ toC₁₅ substituted aryl group. In further embodiments, R⁴ and R⁵independently can be a C₁ to C₅ alkyl group. Substituents (general andspecific) are independently disclosed herein and can be utilized withoutlimitation to further describe substituted groups which can be utilizedas R⁴ and/or R⁵.

In a further aspect, R⁴ and/or R⁵ independently can be a methyl group,an ethyl group, a propyl group, a butyl group, a pentyl group, a hexylgroup, a heptyl group, an octyl group, a nonyl group, or a decyl group.In some embodiments, R⁴ and/or R⁵ independently can be a methyl group,an ethyl group, an n-propyl group, an iso-propyl group, an n-butylgroup, an iso-butyl group, a sec-butyl group, a tert-butyl group, ann-pentyl group, an iso-pentyl group, a sec-pentyl group, or a neopentylgroup; alternatively, a methyl group, an ethyl group, an iso-propylgroup, a tert-butyl group, or a neopentyl group; alternatively, a methylgroup, an ethyl group, an n-propyl group, an n-butyl group, an n-pentylgroup, or an n-hexyl group; alternatively, a methyl group;alternatively, an ethyl group; alternatively, an n-propyl group;alternatively, an iso-propyl group; alternatively, an n-butyl group;alternatively, a tert-butyl group; alternatively, an n-pentyl group;alternatively, a neopentyl group; or alternatively, an n-hexyl group. Insome embodiments, the alkyl groups which can be utilized as R⁴ and/or R⁵can be substituted. Each substituent of a substituted alkyl groupindependently can be a halogen or a hydrocarboxy group; alternatively, ahalogen; or alternatively, a hydrocarboxy group. Halogens, andhydrocarboxy groups (general and specific) are independently disclosedherein (e.g., as general substituents and/or as substituents forsubstituted R¹ groups) and can be utilized without limitation to furtherdescribe the substituted alkyl group which can be utilized as R⁴ and/orR⁵.

In a further aspect, R⁴ and R⁵ independently can be a cyclobutyl group,a substituted cyclobutyl group, a cyclopentyl group, a substitutedcyclopentyl group, a cyclohexyl group, a substituted cyclohexyl group, acycloheptyl group, a substituted cycloheptyl group, a cyclooctyl group,or a substituted cyclooctyl group. In some embodiments, R⁴ and/or R⁵independently can be a cyclopentyl group, a substituted cyclopentylgroup, a cyclohexyl group, or a substituted cyclohexyl group. In otherembodiments, R⁴ and/or R⁵ can be a cyclopentyl group or a substitutedcyclopentyl group; or alternatively, a cyclohexyl group or a substitutedcyclohexyl group. In further embodiments, R⁴ and/or R⁵ independently canbe a cyclopentyl group; alternatively, a substituted cyclopentyl group;a cyclohexyl group; or alternatively, a substituted cyclohexyl group.Substituents (general and specific) are independently disclosed hereinand can be utilized without limitation to further describe thesubstituted cycloalkyl group which can be utilized as R⁴ and/or R⁵.

In an aspect, R⁴ can have Structure G7:

wherein, the undesignated valency is attached to the phosphorus atom ofthe N²-phosphinyl formamidine group. Generally, R^(41c), R^(42c),R^(43c), R^(44c), and R^(45c) independently can be hydrogen or anon-hydrogen substituent, and n can be an integer from 1 to 5. In anembodiment wherein R⁴ has Structure G7, R^(41c), R^(43c), R^(44c), andR^(45c) can be hydrogen and R^(32c) can be any non-hydrogen substituentdisclosed herein; or alternatively, R^(41c), R^(43c), and R^(45c) can behydrogen and R^(42c) and R^(44c) independently can be any non-hydrogensubstituent disclosed herein. In an embodiment, n can be an integer from1 to 4; or alternatively, from 2 to 4. In other embodiments, n can be 2or 3; alternatively, 2; or alternatively 3. Substituents (general andspecific) are independently disclosed herein and can be utilized withoutlimitation to further describe a non-hydrogen substituent which can beutilized without limitation as R^(41c), R^(42c), R^(43c), R^(44c),and/or R^(45c) for the R⁴ group having Structure G7.

In an aspect, R⁵ can have Structure G8:

wherein, the undesignated valency is attached to the phosphorus atom ofthe N²-phosphinyl formamidine group. Generally, R^(51c), R^(52c),R^(53c), R^(54c), and R^(55c) independently can be hydrogen or anon-hydrogen substituent, and n can be an integer from 1 to 5. In anembodiment wherein R⁵ has Structure G8, R^(51c), R^(53c), R^(54c), andR^(55c) can be hydrogen and R^(32c) can be any non-hydrogen substituentdisclosed herein; or alternatively, R^(51c), R^(53c), and R^(55c) can behydrogen and R^(52c) and R^(54c) independently can be any non-hydrogensubstituent disclosed herein. In an embodiment, n can be an integer from1 to 4; or alternatively, from 2 to 4. In other embodiments, n can be 2or 3; alternatively, 2; or alternatively 3. Substituents (general andspecific) are independently disclosed herein and can be utilized withoutlimitation to further describe a non-hydrogen substituent which can beutilized without limitation as R^(51c), R^(52c), R^(53c), R^(54c),and/or R^(55c) for the R⁵ group having Structure G8.

In an aspect, R⁴ and/or R⁵ independently can be a phenyl group, asubstituted phenyl group, a naphthyl group, or a substituted naphthylgroup. In an embodiment, R⁴ and R⁵ independently can be a phenyl groupor a substituted phenyl group; alternatively, a naphthyl group or asubstituted naphthyl group; alternatively, a phenyl group or a naphthylgroup; or alternatively, a substituted phenyl group or a substitutednaphthyl group. In some embodiments, R⁴ and/or R⁵ independently can be aphenyl group; alternatively, a substituted phenyl group; alternatively,a naphthyl group; or alternatively, a substituted naphthyl group.Substituents (general and specific) are independently disclosed hereinand can be utilized without limitation to further describe anysubstituted phenyl group and/or substituted naphthyl group which can beutilized as R⁴ and/or R⁵.

In an embodiment, the R⁴ and/or R⁵ substituted phenyl group can be a2-substituted phenyl group, a 3-substituted phenyl group, a4-substituted phenyl group, a 2,4-disubstituted phenyl group, a2,6-disubstituted phenyl group, a 3,5-disubstituted phenyl group, or a2,4,6-trisubstituted phenyl group. In other embodiments, the R⁴ and/orR⁵ substituted phenyl group can be a 2-substituted phenyl group, a4-substituted phenyl group, a 2,4-disubstituted phenyl group, a2,6-disubstituted phenyl group, or a 2,4,6-trisubstituted phenyl group;alternatively, a 2-substituted phenyl group, a 4-substituted phenylgroup, a 2,4-disubstituted phenyl group, or a 2,6-disubstituted phenylgroup; alternatively, a 3-substituted phenyl group or a3,5-disubstituted phenyl group; alternatively, a 2-substituted phenylgroup or a 4-substituted phenyl group; alternatively, a2,4-disubstituted phenyl group, a 2,6-disubstituted phenyl group, or a2,4,6-trisubstituted phenyl group; alternatively, a 2,6-disubstitutedphenyl group or a 2,4,6-trisubstituted phenyl group; alternatively, a2,4-disubstituted phenyl group or a 2,6-disubstituted phenyl group;alternatively, a 2-substituted phenyl group; alternatively, a3-substituted phenyl group; alternatively, a 4-substituted phenyl group;alternatively, a 2,4-disubstituted phenyl group; alternatively, a2,6-disubstituted phenyl group; alternatively, a 3,5-disubstitutedphenyl group; or alternatively, a 2,4,6-trisubstituted phenyl group.Substituents (general and specific) are independently disclosed hereinand can be utilized without limitation to further describe anysubstituted phenyl group which can be utilized as R⁴ and/or R⁵.

In an embodiment, R⁴ and/or R⁵ independently can be a naphth-1-yl group,a substituted naphth-1-yl group, a naphth-2-yl group, or a substitutednaphth-2-yl group. In some embodiments, R⁴ and/or R⁵ independently canbe a naphth-1-yl group or a substituted naphth-1-yl group;alternatively, a naphth-2-yl group or a substituted naphth-2-yl group;alternatively, a naphth-1-yl group; alternatively, a substitutednaphth-1-yl group; alternatively, a naphth-2-yl group; or alternatively,a substituted naphth-2-yl group. In other embodiments, R⁴ and/or R⁵independently can be a 2-substituted naphth-1-yl group, a 3-substitutednaphth-1-yl group, a 4-substituted naphth-1-yl group, or a 8-substitutednaphth-1-yl group; alternatively, a 2-substituted naphth-1-yl group;alternatively, a 3-substituted naphth-1-yl group; alternatively, a4-substituted naphth-1-yl group; or alternatively, a 8-substitutednaphth-1-yl group. In further embodiments, R⁴ and/or R⁵ independentlycan be a 1-substituted naphth-2-yl group, a 3-substituted naphth-2-ylgroup, a 4-substituted naphth-2-yl group, or a 1,3-disubstitutednaphth-2-yl group; alternatively, a 1-substituted naphth-2-yl group;alternatively, a 3-substituted naphth-2-yl group; alternatively, a4-substituted naphth-2-yl group; alternatively, a 1,3-disubstitutednaphth-2-yl group. Substituents (general and specific) are independentlydisclosed herein and can be utilized without limitation to furtherdescribe any substituted naphthyl group which can be utilized as R⁴and/or R⁵.

In an aspect, R⁴ have Structure G9:

wherein the undesignated valency is attached to the phosphorus atom ofthe N²-phosphinyl formamidine group. Generally, R⁴², R⁴³, R⁴⁴, R⁴⁵, andR⁴⁶ can independently be a hydrogen or a non-hydrogen substituent. In anembodiment wherein R⁴ has Structure G9, R⁴², R⁴³, R⁴⁴, R⁴⁵, and R⁴⁶ canbe hydrogen, R⁴³, R⁴⁴, R⁴⁵, and R⁴⁶ can be hydrogen and R⁴² can be anon-hydrogen substituent, R⁴², R⁴⁴, R⁴⁵, and R⁴⁶ can be hydrogen and R⁴³can be a non-hydrogen substituent, R⁴², R⁴³, R⁴⁵, and R⁴⁶ can behydrogen and R⁴⁴ can be a non-hydrogen substituent, R⁴³, R⁴⁵, and R⁴⁶can be hydrogen and R⁴² and R⁴⁴ can be non-hydrogen substituents, R⁴³,R⁴⁴, and R⁴⁵ can be hydrogen and R⁴² and R⁴⁶ can be non-hydrogensubstituents, R⁴², R⁴⁴, and R⁴⁶ can be hydrogen and R⁴³ and R⁴⁵ can benon-hydrogen substituents, or R⁴³ and R⁴⁵ can be hydrogen and R⁴², R⁴⁴,and R⁴⁶ can be non-hydrogen substituents. In some embodiments wherein R⁴has Structure G9, R⁴³, R⁴⁴, R⁴⁵, and R⁴⁶ can be hydrogen and R⁴² can bea non-hydrogen substituent, R⁴², R⁴³, R⁴⁵, and R⁴⁶ can be hydrogen andR⁴⁴ can be a non-hydrogen substituent, R⁴³, R⁴⁵, and R⁴⁶ can be hydrogenand R⁴² and R⁴⁴ can be non-hydrogen substituents, R⁴³, R⁴⁴, and R⁴⁵ canbe hydrogen and R⁴² and R⁴⁶ can be non-hydrogen substituents, or R⁴³ andR⁴⁵ can be hydrogen and R⁴², R⁴⁴, and R⁴⁶ can be non-hydrogensubstituents; alternatively, R⁴³, R⁴⁴, R⁴⁵, and R⁴⁶ can be hydrogen andR⁴² can be a non-hydrogen substituent, R⁴², R⁴³, R⁴⁵, and R⁴⁶ can behydrogen and R⁴⁴ can be a non-hydrogen substituent, R⁴³, R⁴⁵, and R⁴⁶can be hydrogen and R⁴² and R⁴⁴ can be non-hydrogen substituents, orR⁴³, R⁴⁴, and R⁴⁵ can be hydrogen and R⁴² and R⁴⁶ can be non-hydrogensubstituents; alternatively, R⁴², R⁴⁴, R⁴⁵, and R⁴⁶ can be hydrogen andR⁴³ can be a non-hydrogen substituent, or R⁴², R⁴⁴, and R⁴⁶ can behydrogen and R⁴³ and R⁴⁵ can be non-hydrogen substituents;alternatively, R⁴³, R⁴⁴, R⁴⁵, and R⁴⁶ can be hydrogen and R⁴² can be anon-hydrogen substituent, or R⁴², R⁴³, R⁴⁵, and R⁴⁶ can be hydrogen andR⁴⁴ can be a non-hydrogen substituent; alternatively, R⁴³, R⁴⁵, and R⁴⁶can be hydrogen and R⁴² and R⁴⁴ can be non-hydrogen substituents, R⁴³,R⁴⁴, and R⁴⁵ can be hydrogen and R⁴² and R⁴⁶ can be non-hydrogensubstituents, or R⁴³ and R⁴⁵ can be hydrogen and R⁴², R⁴⁴, and R⁴⁶ canbe non-hydrogen substituents; or alternatively, R⁴³, R⁴⁵, and R⁴⁶ can behydrogen and R⁴² and R⁴⁴ can be non-hydrogen substituents, or R⁴³, R⁴⁴,and R⁴⁵ can be hydrogen and R⁴² and R⁴⁶ can be non-hydrogensubstituents. In other embodiments wherein R⁴ has Structure G9, R⁴²,R⁴³, R⁴⁴, R⁴⁵, and R⁴⁶ can be hydrogen; alternatively, R⁴³, R⁴⁴, R⁴⁵,and R⁴⁶ can be hydrogen and R⁴² can be a non-hydrogen substituent;alternatively, R⁴², R⁴⁴, R⁴⁵, and R⁴⁶ can be hydrogen and R⁴³ can be anon-hydrogen substituent; alternatively, R⁴², R⁴³, R⁴⁵, and R⁴⁶ can behydrogen and R⁴⁴ can be a non-hydrogen substituent; alternatively, R⁴³,R⁴⁵, and R⁴⁶ can be hydrogen and R⁴² and R⁴⁴ can be non-hydrogensubstituents; alternatively, R⁴³, R⁴⁴, and R⁴⁵ can be hydrogen and R⁴²and R⁴⁶ can be non-hydrogen substituents; alternatively, R⁴², R⁴⁴, andR⁴⁶ can be hydrogen and R⁴³ and R⁴⁵ and can be non-hydrogensubstituents; or alternatively, R⁴³ and R⁴⁵ can be hydrogen and R⁴²,R⁴⁴, and R⁴⁶ can be non-hydrogen substituents. Substituents (general andspecific) are independently disclosed herein and can be utilized withoutlimitation as R⁴², R⁴³, R⁴⁴, R⁴⁵, and R⁴⁶ for the R⁴ group havingStructure G9.

In an aspect, R⁵ can have Structure G10:

wherein the undesignated valency is attached to the phosphorus atom ofthe N²-phosphinyl formamidine group. Generally, R⁵², R⁵³, R⁵⁴, R⁵⁵, andR⁵⁶ independently can be hydrogen or a non-hydrogen substituent. In anembodiment wherein R⁵ has Structure G10, R⁵², R⁵³, R⁵⁴, R⁵⁵, and R⁵⁶ canbe hydrogen, R⁵³, R⁵⁴, R⁵⁵, and R⁵⁶ can be hydrogen and R⁵² can be anon-hydrogen substituent, R⁵², R⁵⁴, R⁵⁵, and R⁵⁶ can be hydrogen and R⁵³can be a non-hydrogen substituent, R⁵², R⁵³, R⁵⁵, and R⁵⁶ can behydrogen and R⁵⁴ can be a non-hydrogen substituent, R⁵³, R⁵⁵, and R⁵⁶can be hydrogen and R⁵² and R⁵⁴ can be non-hydrogen substituents, R⁵³,R⁵⁴, and R⁵⁵ can be hydrogen and R⁵² and R⁵⁶ can be non-hydrogensubstituents, R⁵², R⁵⁴, and R⁵⁶ can be hydrogen and R⁵³ and R⁵⁵ can benon-hydrogen substituents, or R⁵³ and R⁵⁵ can be hydrogen and R⁵², R⁵⁴,and R⁵⁶ can be non-hydrogen substituents. In some embodiments wherein R⁵has Structure G10, R⁵³, R⁵⁴, R⁵⁵, and R⁵⁶ can be hydrogen and R⁵² can bea non-hydrogen substituent, R⁵², R⁵³, R⁵⁵, and R⁵⁶ can be hydrogen andR⁵⁴ can be a non-hydrogen substituent, R⁵³, R⁵⁵, and R⁵⁶ can be hydrogenand R⁵² and R⁵⁴ can be non-hydrogen substituents, R⁵³, R⁵⁴, and R⁵⁵ canbe hydrogen and R⁵² and R⁵⁶ can be non-hydrogen substituents, or R⁵³ andR⁵⁵ can be hydrogen and R⁵², R⁵⁴, and R⁵⁶ can be non-hydrogensubstituents; alternatively, R⁵³, R⁵⁴, R⁵⁵, and R⁵⁶ can be hydrogen andR⁵² can be a non-hydrogen substituent, R⁵², R⁵³, R⁵⁵, and R⁵⁶ can behydrogen and R⁵⁴ can be a non-hydrogen substituent, R⁵³, R⁵⁵, and R⁵⁶can be hydrogen and R⁵² and R⁵⁴ can be non-hydrogen substituents, orR⁵³, R⁵⁴, and R⁵⁵ can be hydrogen and R⁵² and R⁵⁶ can be non-hydrogensubstituents; alternatively, R⁵², R⁵⁴, R⁵⁵, and R⁵⁶ can be hydrogen andR⁵³ can be a non-hydrogen substituent, or R⁵², R⁵⁴, and R⁵⁶ can behydrogen and R⁵³ and R⁵⁵ can be non-hydrogen substituents;alternatively, R⁵³, R⁵⁴, R⁵⁵, and R⁵⁶ can be hydrogen and R⁵² can be anon-hydrogen substituent, or R⁵², R⁵³, R⁵⁵, and R⁵⁶ can be hydrogen andR⁵⁴ can be a non-hydrogen substituent; alternatively, R⁵³, R⁵⁵, and R⁵⁶can be hydrogen and R⁵² and R⁵⁴ can be non-hydrogen substituents, R⁵³,R⁵⁴, and R⁵⁵ can be hydrogen and R⁵² and R⁵⁶ can be non-hydrogensubstituents, or R⁵³ and R⁵⁵ can be hydrogen and R⁵², R⁵⁴, and R⁵⁶ canbe non-hydrogen substituents; or alternatively, R⁵³, R⁵⁵, and R⁵⁶ can behydrogen and R⁵² and R⁵⁴ can be non-hydrogen substituents, or R⁵³, R⁵⁴,and R⁵⁵ can be hydrogen and R⁵² and R⁵⁶ can be non-hydrogensubstituents. In other embodiments wherein R⁵ has Structure G10, R⁵²,R⁵³, R⁵⁴, R⁵⁵, and R⁵⁶ can be hydrogen; alternatively, R⁵³, R⁵⁴, R⁵⁵,and R⁵⁶ can be hydrogen and R⁵² can be a non-hydrogen substituent;alternatively, R⁵², R⁵⁴, R⁵⁵, and R⁵⁶ can be hydrogen and R⁵³ can be anon-hydrogen substituent; alternatively, R⁵², R⁵³, R⁵⁵, and R⁵⁶ can behydrogen and R⁵⁴ can be a non-hydrogen substituent; alternatively, R⁵³,R⁵⁵, and R⁵⁶ can be hydrogen and R⁵² and R⁵⁴ can be non-hydrogensubstituents; alternatively, R⁵³, R⁵⁴, and R⁵⁵ can be hydrogen and R⁵²and R⁵⁶ can be non-hydrogen substituents; alternatively, R⁵², R⁵⁴, andR⁵⁶ can be hydrogen and R⁵³ and R⁵⁵ and can be non-hydrogensubstituents; or alternatively, R⁵³ and R⁵⁵ can be hydrogen and R⁵²,R⁵⁴, and R⁵⁶ can be non-hydrogen substituents. Substituents (general andspecific) are independently disclosed herein and can be utilized withoutlimitation as R⁵², R⁵³, R⁵⁴, R⁵⁵, and R⁵⁶ for the R⁵ group havingStructure G10.

In an aspect, R⁴ and R⁵ can be joined to form a cyclic group includingthe phosphorus atom. In an embodiment when R⁴ and R⁵ are joined to forma cyclic group including the phosphorus atom of the N²-phosphinylformamidine group, the phosphinyl group can be a phosphol-1-yl group, asubstituted phosphol-1-yl group, a 2,3-dihydrophosphol-1-yl group, asubstituted 2,3-dihydrophosphol-1-yl group, a 3,5-dihydrophosphol-1-ylgroup, a substituted 3,5-dihydrophosphol-1-yl group, a phospholan-1-ylgroup, a substituted phospholan-1-yl group, a 1,2-dihydrophosphinin-1-ylgroup, a substituted, 1,2-dihydrophosphinin-1-yl group, a1,4-dihydrophosphinin-1-yl group, a substituted1,4-dihydrophosphinin-1-yl group, a 1,2,3,4-tetrahydrophosphinin-1-ylgroup, a substituted 1,2,3,4-tetrahydrophosphinin-1-yl group, a1,2,3,6-tetrahydrophosphinin-1-yl group, a substituted1,2,3,6-tetrahydrophosphinin-1-yl group, a phosphinan-1-yl group, or asubstituted phosphinan-1-yl group. In some embodiments, when R⁴ and R⁵are joined to form a cyclic group including the phosphorus atom of theN²-phosphinyl formamidine group, the phosphinyl group can be aphosphol-1-yl group or a substituted phosphol-1-yl group; alternatively,a 2,3-dihydrophosphol-1-yl group or a substituted2,3-dihydrophosphol-1-yl group; alternatively, a3,5-dihydrophosphol-1-yl group or a substituted 3,5-dihydrophosphol-1-ylgroup; alternatively, a phospholan-1-yl group or a substitutedphospholan-1-yl group; alternatively, a 1,2-dihydrophosphinin-1-yl groupor a substituted, 1,2-dihydrophosphinin-1-yl group; alternatively, a1,4-dihydrophosphinin-1-yl group or a substituted1,4-dihydrophosphinin-1-yl group; alternatively, a1,2,3,4-tetrahydrophosphinin-1-yl group or a substituted1,2,3,4-tetrahydrophosphinin-1-yl group; alternatively, a1,2,3,6-tetrahydrophosphinin-1-yl group or a substituted1,2,3,6-tetrahydrophosphinin-1-yl group; or alternatively, aphosphinan-1-yl group or a substituted phosphinan-1-yl group. In someembodiments, when R⁴ and R⁵ are joined to form a cyclic group includingthe phosphorus atom of the N²-phosphinyl formamidine group, thephosphinyl group can be a phosphol-1-yl group, a2,3-dihydrophosphol-1-yl group, a 3,5-dihydrophosphol-1-yl group, aphospholan-1-yl group, a 1,2-dihydrophosphinin-1-yl group, a1,4-dihydrophosphinin-1-yl group, a 1,2,3,4-tetrahydrophosphinin-1-ylgroup, a 1,2,3,6-tetrahydrophosphinin-1-yl group, or a phosphinan-1-ylgroup. In other embodiments, when R⁴ and R⁵ are joined to form a cyclicgroup including the phosphorus atom of the N²-phosphinyl formamidinegroup, the phosphinyl group can be a substituted phosphol-1-yl group, asubstituted 2,3-dihydrophosphol-1-yl group, a substituted3,5-dihydrophosphol-1-yl group, a substituted phospholan-1-yl group, asubstituted, 1,2-dihydrophosphinin-1-yl group, a substituted1,4-dihydrophosphinin-1-yl group, a substituted1,2,3,4-tetrahydrophosphinin-1-yl group, a substituted1,2,3,6-tetrahydrophosphinin-1-yl group, or a substitutedphosphinan-1-yl group. In yet other embodiments, when R⁴ and R⁵ arejoined to form a cyclic group including the phosphorus atom of theN²-phosphinyl formamidine group a phospholan-1-yl group, a substitutedphospholan-1-yl group, a phosphinan-1-yl group, or a substitutedphosphinan-1-yl group; alternatively, a phospholan-1-yl group or aphosphinan-1-yl group; or alternatively, a substituted phospholan-1-ylgroup or a substituted phosphinan-1-yl group. In further embodiments,when R⁴ and R⁵ are joined to form a cyclic group including thephosphorus atom of the N²-phosphinyl formamidine group, the phosphinylgroup can be a phosphol-1-yl group; alternatively, a substitutedphosphol-1-yl group; alternatively, a 2,3-dihydrophosphol-1-yl group;alternatively, a substituted 2,3-dihydrophosphol-1-yl group;alternatively, a 3,5-dihydrophosphol-1-yl group; alternatively, asubstituted 3,5-dihydrophosphol-1-yl group; alternatively, aphospholan-1-yl group; alternatively, a substituted phospholan-1-ylgroup; alternatively, a 1,2-dihydrophosphinin-1-yl group; alternatively,a substituted, 1,2-dihydrophosphinin-1-yl group; alternatively, a1,4-dihydrophosphinin-1-yl group; alternatively, a substituted1,4-dihydrophosphinin-1-yl group; alternatively, a1,2,3,4-tetrahydrophosphinin-1-yl group; alternatively, a substituted1,2,3,4-tetrahydrophosphinin-1-yl group; alternatively, a1,2,3,6-tetrahydrophosphinin-1-yl group; alternatively, a substituted1,2,3,6-tetrahydrophosphinin-1-yl group; alternatively, aphosphinan-1-yl group; or alternatively, a substituted phosphinan-1-ylgroup. Substituents (general and specific) are independently disclosedherein and can be utilized without limitation to further describesubstituted groups where R⁴ and R⁵ are joined to form a cyclic groupincluding the phosphorus atom.

In an embodiment, when R⁴ and R⁵ are joined to form a cyclic groupincluding the phosphorus atom of the N²-phosphinyl formamidine group,the cyclic group including the phosphorus atom can comprise at least onesubstituent on a carbon atom adjacent to the phosphorus atom attached tothe N² nitrogen atom of the N²-phosphinyl formamidine group. In someembodiments, when R⁴ and R⁵ are joined to form a cyclic group includingthe phosphorus atom of the N²-phosphinyl formamidine group, the cyclicgroup including the phosphorus atom can comprise at least onesubstituent on each carbon atom adjacent to the phosphorus atom attachedto the N² nitrogen atom of the N²-phosphinyl formamidine group. In otherembodiments, when R⁴ and R⁵ are joined to form a cyclic group includingthe phosphorus atom of the N²-phosphinyl formamidine group, the cyclicgroup including the phosphorus atom can comprise, or consist of, onlyone substituent on a carbon atom adjacent to the phosphorus atomattached to the N² nitrogen atom of the N²-phosphinyl formamidine group.In yet other embodiments, when R⁴ and R⁵ are joined to form a cyclicgroup including the phosphorus atom of the N²-phosphinyl formamidinegroup, the cyclic group including the phosphorus atom can comprise, orconsist of, only one substituent on each carbon atom adjacent to thephosphorus atom attached to the N² nitrogen atom of the N²-phosphinylformamidine group. Substituents (general and specific) are independentlydisclosed herein and can be utilized without limitation to furtherdescribe substituted group(s) where R⁴ and R⁵ are joined to form acyclic group including the phosphorus atom.

In an embodiment, R⁴ and/or R⁵ independently can be a phenyl group, a2-alkylphenyl group, a 3-alkylphenyl group, a 4-alkylphenyl group, a2,4-dialkylphenyl group, a 2,6-dialkylphenyl group, a 3,5-dialkylphenylgroup, or a 2,4,6-trialkylphenyl group; alternatively, a 2-alkylphenylgroup, a 4-alkylphenyl group, a 2,4-dialkylphenyl group, a2,6-dialkylphenyl group, or a 2,4,6-trialkylphenyl group; alternatively,a 2-alkylphenyl group or a 4-alkylphenyl group; alternatively, a2,4-dialkylphenyl group, a 2,6-dialkylphenyl group, or a2,4,6-trialkylphenyl group; alternatively, a 2,4-dialkylphenyl group ora 2,6-dialkylphenyl group; alternatively, a 2,6-dialkylphenyl group, ora 2,4,6-trialkylphenyl group; alternatively, a 3-alkylphenyl group or a3,5-dialkylphenyl group; alternatively, a 2-alkylphenyl group or a2,6-dialkylphenyl group; alternatively, a 2-alkylphenyl group;alternatively, a 3-alkylphenyl group; alternatively, a 4-alkylphenylgroup; alternatively, a 2,4-dialkylphenyl group; alternatively, a2,6-dialkylphenyl group; alternatively, a 3,5-dialkylphenyl group; oralternatively, a 2,4,6-trialkylphenyl group. In another non-limitingembodiment, R⁴ and/or R⁵ independently can be a napht-1-yl group, a2-naphth-2-yl group, a 2-alkylnaphth-1-yl group, a 1-alkylnaphth-2-ylgroup, a 3-alkylnapth-2-yl group, or a 1,3-dialkylnaphth-2-yl group;alternatively, a napht-1-yl group or a 2-alkylnaphth-1-yl group;alternatively, a naphth-2-yl group, a 1-alkylnaphth-2-yl group, a3-alkylnapth-2-yl group, or a 1,3-dialkylnaphth-2-yl group;alternatively, a napht-1-yl group; alternatively, a 2-naphth-2-yl group;alternatively, a 2-alkylnaphth-1-yl group; alternatively, a1-alkylnaphth-2-yl group; alternatively, a 3-alkylnapth-2-yl group; oralternatively, a 1,3-dialkylnaphth-2-yl group. In other non-limitingembodiments, R⁴ and/or R⁵ independently can be a cyclohexyl group, a2-alkylcyclohexyl group, or a 2,6-dialkylcyclohexyl group;alternatively, a cyclopentyl group, a 2-alkylcyclopentyl group, or a2,5-dialkylcyclopentyl group; alternatively, a cyclohexyl group;alternatively, a 2-alkylcyclohexyl group; alternatively, a2,6-dialkylcyclohexyl group; alternatively, cyclopentyl group;alternatively, a 2-alkylcyclopentyl group; or alternatively, a2,5-dialkylcyclopentyl group. Alkyl group substituents (general andspecific) are independently described herein and can be utilized,without limitation, to further describe the alkylphenyl, dialkylphenyl,trialkylphenyl, naphthyl, dialkylnaphthyl, alkylcyclohexyl,dialkylcyclohexyl, alkylcyclopentyl, or dialkylcyclopentyl groups thatcan be utilized as R⁴ and/or R⁵. Generally, the alkyl substituents of adialkyl or trialkyl phenyl, naphthyl, cyclohexyl, or cyclopentyl groupcan be the same; or alternatively the alkyl substituents of a dialkyl ortrialkyl phenyl, naphthyl, cyclohexyl, or cyclopentyl group can bedifferent.

In another non-limiting embodiment, R⁴ and/or R⁵ independently can be aphenyl group, a 2-alkoxyphenyl group, a 3-alkoxyphenyl group, a4-alkoxyphenyl group, or a 3,5-dialkoxyphenyl group; alternatively, a2-alkoxyphenyl group or a 4-alkoxyphenyl group; alternatively, a3-alkoxyphenyl group or a 3,5-dialkoxyphenyl group; alternatively, a2-alkoxyphenyl group, alternatively, a 3-alkoxyphenyl group;alternatively, a 4-alkoxyphenyl group; alternatively, a3,5-dialkoxyphenyl group. Alkoxy group substituents (general andspecific) are independently described herein and can be utilized,without limitation, to further describe the alkoxyphenyl ordialkoxyphenyl groups that can be utilized as R⁴ and/or R⁵. Generally,the alkoxy substituents of a dialkoxyphenyl groups can be the same; oralternatively the alkoxy substituents of a dialkoxyphenyl group can bedifferent.

In other non-limiting embodiments, R⁴ and/or R⁵ independently can be aphenyl group, a 2-halophenyl group, a 3-halophenyl group, a 4-halophenylgroup, a 2,6-dihalophenyl group, or a 3,5-dialkylphenyl group;alternatively, a 2-halophenyl group, a 4-halophenyl group, or a2,6-dihalophenyl group; alternatively, a 2-halophenyl group or a4-halophenyl group; alternatively, a 3-halophenyl group or a3,5-dihalophenyl group; alternatively, a 2-halophenyl group;alternatively, a 3-halophenyl group; alternatively, a 4-halophenylgroup; alternatively, a 2,6-dihalophenyl group; or alternatively, a3,5-dihalophenyl group. Halides are independently described herein andcan be utilized, without limitation, to further describe the halophenylor dihalophenyl groups that can be utilized R⁴ and/or R⁵. Generally, thehalides of a dihalophenyl group can be the same; or alternatively thehalides of a dihalophenyl group can be different.

In a non-limiting embodiment, R⁴ and/or R⁵ independently can be a2-methylphenyl group, a 2-ethylphenyl group, a 2-isopropylphenyl group,a 2-tert-butylphenyl group, a 3-methylphenyl group, a 2,6-dimethylphenylgroup, a 2,6-diethylphenyl group, a 2,6-diisopropylphenyl group, a2,6-di-tert-butyl-phenyl group, a 3,5-dimethyl group, or a2,4,6-trimethylphenyl group; alternatively, a 2-methylphenyl group, a2-ethylphenyl group, a 2-isopropylphenyl group, or a 2-tert-butylphenylgroup; alternatively, a 2,6-dimethylphenyl group, a 2,6-diethylphenylgroup, a 2,6-diisopropylphenyl group, or a 2,6-di-tert-butylphenylgroup; alternatively, 2-methylphenyl group; alternatively, a2-ethylphenyl group; alternatively, a 2-isopropylphenyl group;alternatively, a 2-tert-butylphenyl group; alternatively, a3-methylphenyl group; alternatively, a 2,6-dimethylphenyl group;alternatively, a 2,6-diethylphenyl group; alternatively, a2,6-diisopropylphenyl group; alternatively, a 2,6-di-tert-butylphenylgroup; alternatively, a 3,5-dimethyl group; or alternatively, a2,4,6-trimethylphenyl group. In another non-limiting embodiment, R⁴and/or R⁵ independently can be a cyclohexyl group, a 2-methylcyclohexylgroup, a 2-ethylcyclohexyl group, a 2-isopropylcyclohexyl group, a2-tert-butylcyclohexyl group, a 2,6-dimethylcyclohexyl group, a2,6-diethylcyclohexyl group, a 2,6-diisopropylcyclohexyl group, or a2,6-di-tert-butylcyclohexyl group; alternatively, a 2-methylcyclohexylgroup, a 2-ethylcyclohexyl group, a 2-isopropylcyclohexyl group, or a2-tert-butylcyclohexyl group; alternatively, a 2,6-dimethylcyclohexylgroup, a 2,6-diethylcyclohexyl group, a 2,6-diisopropylcyclohexyl group,or a 2,6-di-tert-butylcyclohexyl group; alternatively, a cyclohexylgroup; alternatively, a 2-methylcyclohexyl group; alternatively, a2-ethylcyclohexyl group; alternatively, a 2-isopropylcyclohexyl group;alternatively, a 2-tert-butylcyclohexyl group; alternatively, a2,6-dimethylcyclohexyl group; alternatively, a 2,6-diethylcyclohexylgroup; alternatively, a 2,6-diisopropylcyclohexyl group; oralternatively, a 2,6-di-tert-butylcyclohexyl group. In anothernon-limiting embodiment, R⁴ and/or R⁵ independently can be a2-methylnaphth-1-yl group, a 2-ethylnaphth-1-yl group, a2-n-propylnaphth-1-yl group, a 2-isopropylnaphth-1-yl group, or a2-tert-butylnaphth-1-yl group; alternatively, a 2-methylnaphth-1-ylgroup; alternatively, a 2-ethylnaphth-1-yl group; alternatively, a2-n-propylnaphth-1-yl group; alternatively, a 2-isopropylnaphth-1-ylgroup; or alternatively, a 2-tert-butylnaphth-1-yl group.

In a non-limiting embodiment, R⁴ and/or R⁵ independently can be a2-methoxyphenyl group, a 2-ethoxyphenyl group, a 2-isopropoxyphenylgroup, a 2-tert-butoxyphenyl group, a 3-methoxyphenyl group, a3-ethoxyphenyl group, a 3-isopropoxyphenyl group, a 3-tert-butoxyphenylgroup, a 4-methoxy-phenyl group, a 4-ethoxyphenyl group, a4-isopropoxyphenyl group, a 4-tert-butoxyphenyl group, a2,4-dimethoxyphenyl group, a 2,4-diethoxyphenyl group, a2,4-diisopropoxyphenyl group, a 2,4-di-tert-butoxyphenyl group, a3,5-dimethoxyphenyl group, a 3,5-diethoxyphenyl group, a3,5-diisopropoxyphenyl group, a 3,5-di-tert-butoxyphenyl group, a2,6-dimethoxyphenyl group, a 2,6-diethoxyphenyl group, a2,6-diisopropoxyphenyl group, a 2,6-di-tert-butoxyphenyl group, or a2,4,6-trimethoxyphenyl group; alternatively, a 2-methoxyphenyl group, a2-ethoxyphenyl group, a 2-isopropoxyphenyl group, or a2-tert-butoxyphenyl group; alternatively, a 3-methoxyphenyl group, a3-ethoxyphenyl group, a 3-isopropoxyphenyl group, or a3-tert-butoxyphenyl group; alternatively, a 4-methoxyphenyl group, a4-ethoxyphenyl group, a 4-isopropoxyphenyl group, or a4-tert-butoxyphenyl group; alternatively, a 2,4-dimethoxyphenyl group, a2,4-diethoxyphenyl group, a 2,4-diisopropoxyphenyl group, or a2,4-di-tert-butoxyphenyl group, alternatively, a 3,5-dimethoxyphenylgroup, a 3,5-diethoxyphenyl group, a 3,5-diisopropoxyphenyl group, or a3,5-di-tert-butoxyphenyl group; or alternatively, a 2,6-dimethoxyphenylgroup, a 2,6-diethoxyphenyl group, a 2,6-diisopropoxyphenyl group, or a2,6-di-tert-butoxyphenyl group. In other non-limiting embodiments, R⁴and/or R⁵ independently can be a 2-methoxyphenyl group; alternatively, a2-ethoxyphenyl group; alternatively, a 2-isopropoxyphenyl group;alternatively, a 2-tert-butoxyphenyl group; alternatively, a3-methoxyphenyl group; alternatively, a 3-ethoxyphenyl group;alternatively, a 3-isopropoxyphenyl group; alternatively, a3-tert-butoxyphenyl group; alternatively, a 4-methoxyphenyl group;alternatively, a 4-ethoxyphenyl group; alternatively, a4-isopropoxyphenyl group; alternatively, a 4-tert-butoxyphenyl group;alternatively, a 2,4-dimethoxyphenyl group; alternatively, a2,4-diethoxyphenyl group; alternatively, a 2,4-diisopropoxyphenyl group;alternatively, a 2,4-di-tert-butoxyphenyl group; alternatively, a3,5-dimethoxyphenyl group; alternatively, a 3,5-diethoxyphenyl group;alternatively, a 3,5-diisopropoxyphenyl group; alternatively, a3,5-di-tert-butoxyphenyl group; alternatively, a 2,6-dimethoxyphenylgroup; alternatively, a 2,6-diethoxyphenyl group; alternatively, a2,6-diisopropoxyphenyl group; alternatively, a 2,6-di-tert-butoxyphenylgroup; or alternatively, a 2,4,6-trimethoxyphenyl group.

In another non-limiting embodiment, R⁴ and/or R⁵ independently can be a2-fluorophenyl group, a 2-chlorophenyl group, a 3-fluorophenyl group, a3-chlorophenyl group, a 4-fluorophenyl group, a 4-chlorophenyl group, a3,5-difluorophenyl group, or a 3,5-dichlorophenyl group; alternatively,a 2-fluorophenyl group or a 2-chlorophenyl group; alternatively, a3-fluorophenyl group or a 3-chlorophenyl group; alternatively, a4-fluorophenyl group or a 4-chlorophenyl group; alternatively, a3,5-difluorophenyl group or a 3,5-dichlorophenyl group; alternatively, a3-fluorophenyl group, a 3-chlorophenyl group, a 3,5-difluorophenyl groupor a 3,5-dichlorophenyl group; or alternatively, a 3-fluorophenyl groupor a 3,5-difluorophenyl group. In another non-limiting embodiment, R⁴and/or R⁵ independently can be a 2-fluorophenyl group; alternatively, a2-chlorophenyl group; alternatively, a 3-fluorophenyl group;alternatively, a 3-chlorophenyl group; alternatively, a 4-fluorophenylgroup; alternatively, a 4-chlorophenyl group; alternatively, a3,5-difluorophenyl group; or alternatively, a 3,5-dichlorophenyl group.

Generally, the R⁴ and/or R⁵ groups of the phosphinyl group independentlycan be any R⁴ or R⁵ group described herein and utilized in anycombination to further describe the phosphinyl group of anyN²-phosphinyl formamidine compound described herein. In an embodiment,R⁴ and R⁵ can be the same. In other embodiments R⁴ and R⁵ can bedifferent.

In an aspect, the phosphinyl group of the N²-phosphinyl formamidinecompound can be a diphenylphosphinyl group, a dialkylphosphinyl group, abis(mono-halo substituted phenyl)phosphinyl group, a bis(mono-alkylsubstituted phenyl)phosphinyl group, or a bis(mono-alkoxy substitutedphenyl)-phosphinyl group; alternatively, a diphenylphosphinyl group;alternatively, a dialkylphosphinyl group; alternatively, a bis(mono-halosubstituted phenyl)phosphinyl group; alternatively, a bis(mono-alkylsubstituted phenyl)phosphinyl group; alternatively, a bis(mono-alkoxysubstituted phenyl)phosphinyl group. In another aspect, the phosphinylgroup of the N²-phosphinyl formamidine compound can be an(alkyl)(phenyl)phosphinyl group, a (mono-halo substitutedphenyl)(phenyl)phosphinyl group, a (mono-alkyl substitutedphenyl)(phenyl)phosphinyl group, a (mono-alkoxy substitutedphenyl)(phenyl)phosphinyl group, a (mono-alkyl substitutedphenyl)(mono-halo substituted phenyl) phosphinyl group, or a (mono-alkylsubstituted phenyl)(mono-alkoxy substituted phenyl) phosphinyl group;alternatively, an (alkyl)(phenyl)phosphinyl group; alternatively, a(mono-halo substituted phenyl)(phenyl)phosphinyl group; alternatively, a(mono-alkyl substituted phenyl)(phenyl)phosphinyl group; alternatively,a (mono-alkoxy substituted phenyl)(phenyl)phosphinyl group;alternatively, a (mono-alkyl substituted phenyl)-(mono-halo substitutedphenyl) phosphinyl group; or alternatively, a (mono-alkyl substitutedphenyl)-(mono-alkoxy substituted phenyl) phosphinyl group. In anotheraspect, the phosphinyl group of the N²-phosphinyl formamidine compoundcan be a bis(dihalo substituted phenyl)phosphinyl group, a bis(dialkylsubstituted phenyl)phosphinyl group, a bis(dialkoxy substitutedphenyl)phosphinyl group, a bis(trialkylphenyl)phosphinyl group, or abis(trialkoxyphenyl)phosphinyl group; alternatively, a bis(dihalosubstituted phenyl)phosphinyl group; alternatively, a bis(dialkylsubstituted phenyl)phosphinyl group; alternatively, a bis(dialkoxysubstituted phenyl)phosphinyl group; alternatively, abis(trialkylphenyl)phosphinyl group; or alternatively, abis(trialkoxyphenyl)phosphinyl group. Halogens, alkyl group substituents(general and specific), and alkoxy group substituents (general andspecific) are independently described herein (e.g., as substituents forsubstituted R¹ groups) and can be utilized, without limitation tofurther describe the phosphinyl group which can be utilized in theN²-phosphinyl formamidine compound.

In a non-limiting aspect, the phosphinyl group of the N²-phosphinylformamidine compound can be a dimethylphosphinyl group, adiethylphosphinyl group, a diisopropylphosphinyl group, adi-tert-butylphosphinyl group, or a di-neo-pentylphosphinyl group. In anon-limiting embodiment, the phosphinyl group of the N²-phosphinylformamidine compound can be a dimethylphosphinyl group; alternatively, adiethyl phosphinyl group; alternatively, a diisopropylphosphinyl group;alternatively, a di-tert-butylphosphinyl group; or alternatively, adi-neo-pentylphosphinyl group. In a non-limiting aspect, the phosphinylgroup of the N²-phosphinyl formamidine compound can be a(methyl)(phenyl)-phosphinyl group, an (ethyl)(phenyl)phosphinyl group, a(isopropyl)(phenyl)phosphinyl group, a (tert-butyl)(phenyl)phosphinylgroup, or a (neo-pentyl)(phenyl)phosphinyl group. In an embodiment, thephosphinyl group of the N²-phosphinyl formamidine compound can be a(methyl)(phenyl)phosphinyl group; alternatively, an (ethyl)(phenyl)phosphinyl group; alternatively, an (isopropyl)(phenyl)phosphinyl group;alternatively, a (tert-butyl)(phenyl)phosphinyl group; or alternatively,a (neo-pentyl)(phenyl)phosphinyl group. In some non-limitingembodiments, the phosphinyl group of the N²-phosphinyl formamidinecompound can be a dicyclopentyl phosphinyl group, a dicyclohexylphosphinyl group; alternatively, a dicyclopentylphosphinyl group; oralternatively, a dicyclohexylphosphinyl group.

In yet another non-limiting aspect, the phosphinyl group of theN²-phosphinyl formamidine compound can be abis(2-fluorophenyl)phosphinyl group, a bis(2-chlorophenyl)phosphinylgroup, a bis(3-fluorophenyl)phosphinyl group, abis(3-chlorophenyl)phosphinyl group, a bis(4-fluorophenyl)-phosphinylgroup, or a bis(4-chlorophenyl)phosphinyl group. In some non-limitingembodiments, the phosphinyl group of the N²-phosphinyl formamidinecompound can be a bis(2-fluorophenyl)phosphinyl group, abis(3-fluorophenyl)phosphinyl group, or a bis(4-fluorophenyl)phosphinylgroup; or alternatively, a bis(2-chlorophenyl)phosphinyl group, abis(3-chlorophenyl)phosphinyl group, or a bis(4-chlorophenyl)-phosphinylgroup. In other non-limiting embodiments, the phosphinyl group of theN²-phosphinyl formamidine compound can be abis(2-fluorophenyl)phosphinyl group; alternatively, abis(2-chlorophenyl)phosphinyl group; alternatively, abis(3-fluorophenyl)phosphinyl group; alternatively, abis(3-chlorophenyl)phosphinyl group; alternatively, abis(4-fluorophenyl)phosphinyl group; or alternatively, abis(4-chlorophenyl)phosphinyl group.

In yet another non-limiting aspect, the phosphinyl group of theN²-phosphinyl formamidine compound can be a(2-fluorophenyl)(phenyl)phosphinyl group, a(2-chlorophenyl)(phenyl)phosphinyl group, a(3-fluorophenyl)(phenyl)phosphinyl group, a(3-chlorophenyl)(phenyl)phosphinyl group, a(4-fluorophenyl)(phenyl)phosphinyl group, or a(4-chlorophenyl)(phenyl)phosphinyl group. In some non-limitingembodiments, the phosphinyl group of the N²-phosphinyl formamidinecompound can be a (2-fluorophenyl)(phenyl)phosphinyl group, a(3-fluorophenyl)(phenyl)phosphinyl group, or a(4-fluoro-phenyl)(phenyl)phosphinyl group; or alternatively, a(2-chlorophenyl)(phenyl)phosphinyl group, a(3-chlorophenyl)(phenyl)phosphinyl group, or a(4-chlorophenyl)(phenyl)phosphinyl group. In other non-limitingembodiments, the phosphinyl group of the N²-phosphinyl formamidinecompound can be a (2-fluorophenyl)(phenyl)phosphinyl group;alternatively, a (2-chlorophenyl)(phenyl)phosphinyl group;alternatively, a (3-fluorophenyl)(phenyl)phosphinyl group;alternatively, a (3-chlorophenyl)(phenyl)-phosphinyl group;alternatively, a (4-fluorophenyl)(phenyl)phosphinyl group; oralternatively, a (4-chlorophenyl)(phenyl)phosphinyl group.

In yet another non-limiting aspect, the phosphinyl group of theN²-phosphinyl formamidine compound can be a diphenylphosphinyl group, abis(2-methylphenyl)phosphinyl group, a bis(2-ethyl-phenyl)phosphinylgroup, a bis(2-isopropylphenyl)phosphinyl group, abis(2-tert-butylphenyl)phosphinyl group, a bis(3-methylphenyl)phosphinylgroup, a bis(3-ethylphenyl)phosphinyl group,bis(3-isopropyl-phenyl)phosphinyl group, abis(3-tert-butylphenyl)phosphinyl group, a diphenylphosphinyl group, abis(4-methylphenyl)phosphinyl group, a bis(4-ethylphenyl)phosphinylgroup, a bis(4-isopropylphenyl)-phosphinyl group, or abis(4-tert-butylphenyl)phosphinyl group. In a non-limiting embodiment,the phosphinyl group of the N²-phosphinyl formamidine compound can be abis(2-methylphenyl)phosphinyl group, a bis(2-ethylphenyl)phosphinylgroup, a bis(2-isopropylphenyl)phosphinyl group, or abis(2-tert-butylphenyl)phosphinyl group; alternatively, adiphenylphosphinyl group, a bis(3-methyl-phenyl)phosphinyl group, abis(3-ethylphenyl)phosphinyl group, a bis(3-isopropylphenyl)phosphinylgroup, or a bis(3-tert-butylphenyl)phosphinyl group; or alternatively, adiphenylphosphinyl group, a bis(4-methylphenyl)phosphinyl group, abis(4-ethylphenyl)phosphinyl group, a bis(4-isopropylphenyl)-phosphinylgroup, or a bis(4-tert-butylphenyl)phosphinyl group. In othernon-limiting embodiments, the phosphinyl group of the N²-phosphinylformamidine compound can be a diphenylphosphinyl group; alternatively, abis(2-methylphenyl)phosphinyl group; alternatively, abis(2-ethylphenyl)phosphinyl group; alternatively, abis(2-isopropylphenyl)phosphinyl group; alternatively, abis(2-tert-butylphenyl)-phosphinyl group; alternatively, abis(3-methylphenyl)phosphinyl group; alternatively, abis(3-ethyl-phenyl)phosphinyl group; alternatively, abis(3-isopropylphenyl)phosphinyl group; alternatively, abis(3-tert-butylphenyl)phosphinyl group; alternatively, adiphenylphosphinyl group; alternatively, a bis(4-methylphenyl)phosphinylgroup; alternatively, a bis(4-ethylphenyl)phosphinyl group;alternatively, a bis(4-isopropylphenyl)phosphinyl group; oralternatively, a bis(4-tert-butylphenyl)phosphinyl group.

In yet another non-limiting aspect, the phosphinyl group of theN²-phosphinyl formamidine compound can be a diphenylphosphinyl group, a(2-methylphenyl)(phenyl)phosphinyl group, a(2-ethyl-phenyl)(phenyl)phosphinyl group, a(2-isopropylphenyl)(phenyl)phosphinyl group, a(2-tert-butyl-phenyl)(phenyl)phosphinyl group, a(3-methylphenyl)(phenyl)phosphinyl group, a(3-ethylphenyl)-(phenyl)phosphinyl group,(3-isopropylphenyl)(phenyl)phosphinyl group, a(3-tert-butylphenyl)-(phenyl)phosphinyl group, a diphenylphosphinylgroup, a (4-methylphenyl)(phenyl)phosphinyl group, a(4-ethylphenyl)(phenyl)phosphinyl group, a(4-isopropylphenyl)(phenyl)phosphinyl group, or a(4-tert-butylphenyl)(phenyl)phosphinyl group. In a non-limitingembodiment, the phosphinyl group of the N²-phosphinyl formamidinecompound can be a (2-methylphenyl)(phenyl)phosphinyl group, a(2-ethylphenyl)(phenyl)phosphinyl group, a(2-isopropylphenyl)(phenyl)phosphinyl group, or a(2-tert-butylphenyl)(phenyl)phosphinyl group; alternatively, adiphenylphosphinyl group, a (3-methylphenyl)(phenyl)phosphinyl group, a(3-ethylphenyl)(phenyl)phosphinyl group, a(3-isopropylphenyl)(phenyl)phosphinyl group, or a(3-tert-butylphenyl)(phenyl)phosphinyl group; or alternatively, adiphenylphosphinyl group, a (4-methylphenyl)(phenyl)phosphinyl group, a(4-ethylphenyl)(phenyl)phosphinyl group, a(4-isopropylphenyl)(phenyl)phosphinyl group, or a(4-tert-butylphenyl)(phenyl)phosphinyl group. In other non-limitingembodiments, the phosphinyl group of the N²-phosphinyl formamidinecompound can be a diphenylphosphinyl group; alternatively, a(2-methylphenyl)(phenyl)phosphinyl group; alternatively, a(2-ethylphenyl)(phenyl)phosphinyl group; alternatively, a(2-isopropylphenyl)(phenyl)phosphinyl group; alternatively, a(2-tert-butylphenyl)(phenyl)phosphinyl group; alternatively, a(3-methylphenyl)(phenyl)phosphinyl group; alternatively, a(3-ethylphenyl)(phenyl)phosphinyl group; alternatively, a(3-isopropylphenyl)(phenyl)phosphinyl group; alternatively, a(3-tert-butylphenyl)(phenyl)phosphinyl group; alternatively, adiphenylphosphinyl group; alternatively, a(4-methylphenyl)(phenyl)phosphinyl group; alternatively, a(4-ethylphenyl)(phenyl)phosphinyl group; alternatively, a(4-isopropylphenyl)(phenyl)phosphinyl group; or alternatively, a(4-tert-butylphenyl)(phenyl)phosphinyl group.

In yet another non-limiting aspect, the phosphinyl group of theN²-phosphinyl formamidine compound can be a diphenylphosphinyl group, abis(2-methoxyphenyl)phosphinyl group, a bis(2-ethoxy-phenyl)phosphinylgroup, a bis(2-isopropoxyphenyl)phosphinyl group, abis(2-tert-butoxyphenyl)-phosphinyl group, abis(3-methoxyphenyl)phosphinyl group, a bis(3-ethoxyphenyl)phosphinylgroup, a bis(3-isopropoxyphenyl)phosphinyl group, abis(3-tert-butoxyphenyl)phosphinyl group, a diphenoxyphosphinyl group, abis(4-methoxyphenyl)phosphinyl group, a bis(4-ethoxyphenyl)phosphinylgroup, bis(4-isopropoxyphenyl)phosphinyl group, or abis(4-tert-butoxyphenyl)phosphinyl group. In a non-limiting embodiment,the phosphinyl group of the N²-phosphinyl formamidine compound can be abis(2-methoxyphenyl)phosphinyl group, a bis(2-ethoxyphenyl)phosphinylgroup, a bis(2-isopropoxy-phenyl)phosphinyl group, or abis(2-tert-butoxyphenyl)phosphinyl group; alternatively, adiphenoxyphosphinyl group, a bis(3-methoxyphenyl)phosphinyl group, abis(3-ethoxyphenyl)phosphinyl group, a bis(3-isopropoxyphenyl)phosphinylgroup, or a bis(3-tert-butoxyphenyl)phosphinyl group; or alternatively,a diphenoxyphosphinyl group, a bis(4-methoxyphenyl)phosphinyl group, abis(4-ethoxy-phenyl)phosphinyl group, abis(4-isopropoxyphenyl)phosphinyl group, or abis(4-tert-butoxyphenyl)-phosphinyl group. In other non-limitingembodiments, the phosphinyl group of the N²-phosphinyl formamidinecompound can be a diphenylphosphinyl group; alternatively, abis(2-methoxyphenyl)phosphinyl group; alternatively, abis(2-ethoxyphenyl)phosphinyl group; alternatively, abis(2-isopropoxyphenyl)phosphinyl group; alternatively, abis(2-tert-butoxyphenyl)phosphinyl group; alternatively, abis(3-methoxyphenyl)phosphinyl group; alternatively, abis(3-ethoxyphenyl)phosphinyl group; alternatively, abis(3-isopropoxyphenyl)phosphinyl group; alternatively, abis(3-tert-butoxyphenyl)phosphinyl group; alternatively, adiphenoxyphosphinyl group; alternatively, abis(4-methoxyphenyl)phosphinyl group; alternatively, abis(4-ethoxyphenyl)phosphinyl group; alternatively, abis(4-isopropoxyphenyl)phosphinyl group; or alternatively, abis(4-tert-butoxyphenyl)phosphinyl group.

In yet another non-limiting aspect, the phosphinyl group of theN²-phosphinyl formamidine compound can be a diphenylphosphinyl group, a(2-methoxyphenyl)(phenyl)phosphinyl group, a(2-ethoxyphenyl)(phenyl)phosphinyl group, a(2-isopropoxyphenyl)(phenyl)phosphinyl group, a(2-tert-butoxyphenyl)(phenyl)phosphinyl group, a(3-methoxyphenyl)(phenyl)phosphinyl group, a(3-ethoxyphenyl)(phenyl)phosphinyl group, a(3-isopropoxyphenyl)(phenyl)phosphinyl group, a(3-tert-butoxyphenyl)(phenyl)phosphinyl group, a diphenoxyphosphinylgroup, a (4-methoxyphenyl)-(phenyl)phosphinyl group, a(4-ethoxyphenyl)(phenyl)phosphinyl group, a(4-isopropoxyphenyl)-(phenyl)phosphinyl group, or a(4-tert-butoxyphenyl)(phenyl)phosphinyl group. In a non-limitingembodiment, the phosphinyl group of the N²-phosphinyl formamidinecompound can be a (2-methoxy-phenyl)(phenyl)phosphinyl group, a(2-ethoxyphenyl)(phenyl)phosphinyl group, a(2-isopropoxyphenyl)-(phenyl)phosphinyl group, or a(2-tert-butoxyphenyl)(phenyl)phosphinyl group; alternatively, adiphenoxyphosphinyl group, a (3-methoxyphenyl)(phenyl)phosphinyl group,a (3-ethoxyphenyl)(phenyl)-phosphinyl group, a(3-isopropoxyphenyl)(phenyl)phosphinyl group, or a(3-tert-butoxyphenyl)(phenyl)-phosphinyl group; or alternatively, adiphenoxyphosphinyl group, a (4-methoxyphenyl)(phenyl)-phosphinyl group,a (4-ethoxyphenyl)(phenyl)phosphinyl group,(4-isopropoxyphenyl)(phenyl)-phosphinyl group, or a(4-tert-butoxyphenyl)(phenyl)phosphinyl group. In other non-limitingembodiments, the phosphinyl group of the N²-phosphinyl formamidinecompound can be a diphenylphosphinyl group; alternatively, a(2-methoxyphenyl)(phenyl)phosphinyl group; alternatively, a(2-ethoxyphenyl)(phenyl)phosphinyl group; alternatively, a(2-isopropoxyphenyl)(phenyl)phosphinyl group; alternatively, a(2-tert-butoxyphenyl)(phenyl)phosphinyl group; alternatively, a(3-methoxy-phenyl)(phenyl)phosphinyl group; alternatively, a(3-ethoxyphenyl)(phenyl)phosphinyl group; alternatively, a(3-isopropoxyphenyl)(phenyl)phosphinyl group; alternatively, a(3-tert-butoxyphenyl)-(phenyl)phosphinyl group; alternatively, adiphenoxyphosphinyl group; alternatively, a(4-methoxy-phenyl)(phenyl)phosphinyl group; alternatively, a(4-ethoxyphenyl)(phenyl)phosphinyl group; alternatively,(4-isopropoxyphenyl)(phenyl)phosphinyl group; or alternatively, a(4-tert-butoxy-phenyl)(phenyl)phosphinyl group.

N²-Phosphinyl Formamidine Metal Salt Complexes

In an aspect, this disclosure provides for an N²-phosphinyl formamidinemetal salt complex. Generally, the N²-phosphinyl formamidine metal saltcomplex can comprise a metal salt complexed to an N²-phosphinylformamidine compound. In some embodiments, the N²-phosphinyl formamidinemetal salt complex can further comprise a neutral ligand, Q. In otherembodiments, the N²-phosphinyl formamidine metal salt complex can bedimeric. N²-phosphinyl formamidine compounds are generally describedherein and can be utilized, without limitation, to further describe theN²-phosphinyl formamidine metal salt complex comprising a metal saltcomplexed to an N²-phosphinyl formamidine compound. In an embodiment,the N²-phosphinyl formamidine metal salt complex can have StructureNPFMC1 or NPFMC2; alternatively, Structure NPFMC1; or alternatively,Structure NPFMC2.

In some embodiments, the the N²-phosphinyl formamidine metal saltcomplex can have Structure NPFMC3 or NPFMC4; alternatively, StructureNPFMC3; or alternatively, Structure NPFMC4.

R¹, R³, R⁴, R⁵, M, X, Q, p, and q within the N²-phosphinyl formamidinemetal salt complex Structures NPFMC1, NPFMC2, NPFMC3, and/or NPFMC4 areindependently described herein and these description can be utilized inany combination to further describe the N²-phosphinyl formamidine metalsalt complexes of this disclosure. Generally, MX_(p) or MX_(p)Q_(q)represents the metal salt of the metal complex, Q represents a neutralligand, and q represents the number of neutral ligands in theN²-phosphinyl formamidine metal salt complex. The N²-phosphinylformamidine compound features R¹, R³, R⁴, and R⁵ are described forN²-phosphinyl formamidine compounds having Structures NPFMC1, NPFMC2,NPFMC3, and/or NPFMC4 can be utilized without limitation to describe theN²-phosphinyl formamidine metal salt complexes having Structures NPFMC1,NPFMC2, NPFMC3, and/or NPFMC4.Metal Salt

Generally, the metal salt, MX_(P) or MX_(p)Q_(q), of the N²-phosphinylformamidine metal salt complex comprising a metal salt complexed to anN²-phosphinyl formamidine compound can comprise a cationic metal, M, andan anionic ligand, X. In some embodiments, the metal salt can furthercomprise a neutral ligand which may or may not be present in theN²-phosphinyl formamidine metal salt complex comprising a metal saltcomplexed to an N²-phosphinyl formamidine compound.

Generally, the metal atom of the metal salt, MX_(p) or MX_(p)Q_(q) canbe any metal atom. In an aspect, the metal atom of the metal salt can bea transition metal. In an embodiment, suitable metal salts can comprise,or consist essentially of, a Group 3-12 transition metal; alternatively,a Group 4-10 transition metal; alternatively, a Group 6-9 transitionmetal; alternatively, a Group 7-8 transition metal; alternatively, aGroup 4 transition metal; alternatively, a Group 5 transition metal,alternatively, a Group 6 transition metal; alternatively, a Group 7transition metal; alternatively, a Group 8 transition metal;alternatively, a Group 9 transition metal; or alternatively, a Group 10transition metal. In some embodiments, the metal salt can comprisetitanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium,molybdenum, tungsten, manganese, iron, cobalt, nickel, palladium,platinum, copper, or zinc. In other embodiments, the metal salt cancomprise titanium, zirconium, vanadium, chromium, molybdenum, tungsten,iron, cobalt, nickel, palladium, or platinum; alternatively, chromium,iron, cobalt, or nickel; alternatively, titanium, zirconium or hafnium;alternatively, vanadium or niobium; alternatively, chromium, molybdenumor tungsten; alternatively, iron or cobalt; or alternatively, nickel,palladium, platinum, copper, or zinc. In other embodiments, the metalsalt can comprise titanium; alternatively, zirconium; alternatively,hafnium; alternatively, vanadium; alternatively, niobium; alternatively,tantalum; alternatively, chromium; alternatively, molybdenum;alternatively, tungsten; alternatively, manganese; alternatively, iron;alternatively, cobalt; alternatively, nickel; alternatively, palladium;alternatively, platinum; alternatively, copper; or alternatively, zinc.

Generally, the metal atom of the transition metal salt can have anypositive oxidation state available to the metal atom. In an embodiment,the transition metal can have an oxidation state of from +2 to +6;alternatively, from +2 to +4; or alternatively, from +2 to +3. In someembodiments, the metal atom of the transition metal salt can have anoxidation state or +1; alternatively, +2; alternatively, +3; oralternatively, +4.

In some embodiments, the anionic ligand can be a monoanionic ligand or adianionic ligand; alternatively, a monoanionic ligand; or alternatively,a dianionic ligand. When the anionic ligand is a monoanionic ligand, themetal salt can have the formula MX_(p) or MX_(p)Q_(q) where M can be anymetal atom described herein, X can be any monoanionic ligand describedherein, Q can be any neutral ligand described herein, q can be anynumber described herein, and p can range from 2 to 6; alternatively,range from 2 to 4; alternatively, range from 2 to 3; alternatively, canbe 1; alternatively, can be 2; alternatively, can be 3; oralternatively, can be 4. In some embodiments where the anionic ligand isa monoanionic ligand, p can equal the oxidation state of the metal atom.

When the anionic ligand is a dianionic ligand the metal salt can havethe formula M_(y)X_(p) or M_(y)X_(p)Q_(q) where M can be any metal atomdescribed herein, y equals 2 divided by the greatest common divisor ofoxidation state of the metal atom and 2, X can be any dianionic liganddescribed herein, p equals the oxidation state of the metal atom dividedby the greatest common divisor of oxidation state of the metal atom and2, Q can be any neutral ligand described herein, and q can be any numberdescribed herein. In some embodiment when the anionic ligand is adianionic ligand, p can range from, 1 to 3; alternatively, range from 1to 2; alternatively, can be 1; alternatively, can be 2; oralternatively, can be 3.

In an embodiment, the monoanionic ligand, X, can be a halide, acarboxylate, a β-diketonate, a hydrocarboxide, a nitrate, or a chlorate.In some embodiments, the monoanionic ligand, X, can be a halide, acarboxylate, a β-diketonate, or a hydrocarboxide. In any aspect orembodiment, the hydrocarboxide can be an alkoxide, an aryloxide, or anaralkoxide. Generally, hydrocarboxide (and subdivisions ofhydrocarboxide) are the anion analogues of the hydrocarboxy group. Inother embodiments, the monoanionic ligand, X, can be a halide, acarboxylate, a β-diketonate, or an alkoxide; or alternatively, a halideor a β-diketonate. In other embodiments, the monoanion X can be ahalide; alternatively, a carboxylate; alternatively, a β-diketonate;alternatively, a hydrocarboxide; alternatively, an alkoxide; oralternatively, an aryloxide.

Generally, each halide monoanion independently can be fluorine,chlorine, bromine, or iodine; or alternatively, chlorine, bromine, oriodine. In an embodiment, each halide monoanion can be chlorine;alternatively, bromine; or alternatively, iodine.

Generally, the carboxylate, a β-diketonate, hydrocarboxide (alsoalkoxide, aryloxide, or aralkoxide) can be any C₁ to C₂₀ carboxylate, aβ-diketonate, hydrocarboxide (also alkoxide, aryloxide or aralkoxide);or alternatively, any C₁ to C₁₀ carboxylate, a β-diketonate,hydrocarboxide (also alkoxide, aryloxide, or aralkoxide). In someembodiments, the monoanionic ligand, X, can be a C₁ to C₂₀ carboxylate;alternatively, a C₁ to C₂₀ carboxylate; alternatively, a C₁ to C₂₀β-diketonate; alternatively, a C₁ to C₁₀ β-diketonate; alternatively, aC₁ to C₂₀ hydrocarboxide; alternatively, a C₁ to C₁₀ hydrocarboxide;alternatively, a C₁ to C₂₀ alkoxide; alternatively, a C₁ to C₁₀alkoxide; alternatively, a C₆ to C₂₀ aryloxide; or alternatively, a C₆to C₁₀ aryloxide.

In an aspect, each carboxylate monoanionic ligand independently can beacetate, a propionate, a butyrate, a pentanoate, a hexanoate, aheptanoate, an octanoate, a nonanoate, a decanoate, an undecanoate, adodecanoate, a tridecanoate, a tetradecanoate, a pentadecanoate, ahexadecanoate, a heptadecanoate, or an octadecanoate; or alternatively,a pentanoate, a hexanoate, a heptanoate, an octanoate, a nonanoate, adecanoate, an undecanoate, or a dodecanoate. In an embodiment, eachcarboxylate monoanionic ligand independently can be acetate, propionate,n-butyrate, valerate (n-pentanoate), neo-pentanoate, capronate(n-hexanoate), n-heptanoate, caprylate (n-octanoate), 2-ethylhexanoate,n-nonanoate, caprate (n-decanoate), n-undecanoate, laurate(n-dodecanoate), or stearate (n-octadecanoate); alternatively, valerate(n-pentanoate), neo-pentanoate, capronate (n-hexanoate), n-heptanoate,caprylate (n-octanoate), 2-ethylhexanoate, n-nonanoate, caprate(n-decanoate), n-undecanoate, or laurate (n-dodecanoate); alternatively,capronate (n-hexanoate); alternatively, n-heptanoate; alternatively,caprylate (n-octanoate); or alternatively, 2-ethylhexanoate. In someembodiments, the carboxylate monoanionic ligand can be triflate(trifluoroacetate).

In an aspect, each β-diketonate monoanionic ligand independently can beacetylacetonate (alternatively 2,4-pentanedionate),hexafluoroacetylacetone (alternatively,1,1,1,5,5,5-hexafluoro-2,4-pentanediuonate, or benzoylacetonate);alternatively, acetylacetonate; alternatively, hexafluoroacetylacetone;or alternatively, benzoylacetonate. In an aspect, each alkoxidemonoanionic ligand independently can be methoxide, ethoxide, apropoxide, or a butoxide. In an embodiment, each alkoxide monoanionicligand independently can be methoxide, ethoxide, isopropoxide, ortert-butoxide; alternatively, methoxide; alternatively, an ethoxide;alternatively, an iso-propoxide; or alternatively, a tert-butoxide. Inan aspect, the aryloxide can be phenoxide.

In an embodiment, the dianionic ligand, X, can be a catecholate or adicarboxylate; alternatively, a catecholate; or alternatively, adicarboxylate. In an embodiment, the catecholate can be a C₆ to C₂₀catecholate; alternatively, C₆ to C₁₅ catecholate; or alternatively, C₆to C₁₀ catecholate. In an embodiment, the dicarboxylate can be a C₂ toC₂₀ dicarboxylate; alternatively, C₂ to C₁₀ dicarboxylate; oralternatively, a C₂ to C₆ dicarboxylate. In some embodiments, thecatecholate can be 1,2-catecholate, or a substituted 1,2-catecholate;alternatively, 1,2-catecholate; or alternatively, a substituted1,2-catecholate.

In some embodiments, the dicarboxylate can be oxalate, a malonate, asuccinate, acetylenedicarboxylate, phthalate, or a substitutedphthalate; alternatively, oxalate, a succinate, phthalate, or asubstituted phthalate; alternatively, oxalate; alternatively, asuccinate; alternatively, phthalate or a substituted phthalate;alternatively, phthalate; or alternatively, a substituted phthalate. Insome embodiments, the dicarboxylate ligand can be oxalate, 1,3propanedioate, 1,4 butanedioate, 1,2-benzene dicarboxylate, or asubstituted 1,2-benzene dicarboxylate; alternatively, 1,2-benzenedicarboxylate or a substituted 1,2-benzene dicarboxylate; alternatively,oxalate; alternatively, 1,3 propanedioate; alternatively, 1,4butanedioate; alternatively, 1,2-benzene dicarboxylate; oralternatively, a substituted 1,2-benzene dicarboxylate. Substituents(general and specific) are independently disclosed herein and can beutilized without limitation to further describe the substituted1,2-benzene dicarboxylates which can be utilized as the dianionicligand.

Neutral Ligand

Generally, each neutral ligand of the transition metal salt or theN²-phosphinyl formamidine metal salt complex comprising a transitionmetal salt complexed to an N²-phosphinyl formamidine compound, ifpresent, independently can be any neutral ligand that forms anisolatable compound of the metal salt or N²-phosphinyl formamidine metalsalt complex comprising a transition metal salt complexed to anN²-phosphinyl formamidine compound. In an aspect, each neutral ligandindependently can be a nitrile or an ether. In an embodiment, theneutral ligand can be a nitrile; or alternatively, an ether. The numberof neutral ligands, q, of the metal salt or N²-phosphinyl formamidinemetal salt complex comprising a transition metal salt complexed to anN²-phosphinyl formamidine compound can be any number that forms anisolatable metal salt or N²-phosphinyl formamidine metal salt complexcomprising a transition metal salt complexed to an N²-phosphinylformamidine compound. In an aspect, the number of neutral ligands, q,can be from 0 to 6, alternatively, from 0 to 3; alternatively, 0,alternatively, 1; alternatively, 2, alternatively, 3; or alternatively,4. It should be noted that the neutral ligand of the N²-phosphinylformamidine metal salt complex comprising a transition metal saltcomplexed to an N²-phosphinyl formamidine compound does not have to bethe same, if present, as the neutral ligand of the transition metal saltused to form the N²-phosphinyl formamidine metal salt complex.Additionally, a metal salt not having a neutral ligand can be utilizedto prepare an N²-phosphinyl formamidine metal salt complex comprising atransition metal salt complexed to an N²-phosphinyl formamidine compoundhaving a neutral ligand.

Generally, each neutral nitrile ligand independently can be a C₂ to C₂₀nitrile; or alternatively, a C₂ to C₁₀ nitrile. In an embodiment, eachneutral nitrile ligand independently can be a C₂-C₂₀ aliphatic nitrile,a C₇-C₂₀ aromatic nitrile, a C₈-C₂₀ aralkane nitrile, or any combinationthereof; alternatively, a C₂-C₂₀ aliphatic nitrile; alternatively, aC₇-C₂₀ aromatic nitrile; or alternatively, a C₈-C₂₀ aralkane nitrile. Insome embodiments, each neutral nitrile ligand independently can be aC₂-C₁₀ aliphatic nitrile, a C₇-C₁₀ aromatic nitrile, a C₈-C₁₀ aralkanenitrile, or any combination thereof; alternatively, a C₁-C₁₀ aliphaticnitrile; alternatively, a C₇-C₁₀ aromatic nitrile; or alternatively, aC₈-C₁₀ aralkane nitrile.

In an embodiment, each aliphatic nitrile independently can beacetonitrile, propionitrile, a butyronitrile, or any combinationthereof; alternatively, acetonitrile; alternatively, propionitrile; oralternatively, a butyronitrile. In an embodiment, each aromatic nitrileindependently can be benzonitrile, 2-methylbenzonitrile,3-methylbenzonitrile, 4-methylbenzonitrile, 2-ethylbenzonitrile,3-ethylbenzonitrile, 4-ethylbenzonitrile, or any combination thereof;alternatively, benzonitrile; alternatively, 2-methylbenzonitrile;alternatively, 3-methylbenzonitrile; alternatively,4-methylbenzonitrile; alternatively, 2-ethylbenzonitrile; alternatively,3-ethylbenzonitrile; or alternatively, 4-ethylbenzonitrile.

Generally, each neutral ether ligand independently can be a C₂ to C₄₀ether; alternatively, a C₂ to C₃₀ ether; or alternatively, a C₂ to C₂₀ether. In an embodiment, neutral ligand independently can be a C₂ to C₄₀aliphatic acyclic ether, a C₃ to C₄₀ aliphatic cyclic ether, a C₄ to C₄₀aromatic cyclic ether, or a C₁₂ to C₄₀ diaryl ether; alternatively, a C₂to C₄₀ aliphatic acyclic ether; alternatively, a C₃ to C₄₀ aliphaticcyclic ether; alternatively, a C₄ to C₄₀ aromatic cyclic ether; oralternatively, a C₁₂ to C₄₀ diaryl ether. In some embodiments, eachneutral ligand independently can be a C₂ to C₃₀ aliphatic acyclic ether,a C₃ to C₃₀ aliphatic cyclic ether, a C₄ to C₃₀ aromatic cyclic ether,or a C₁₂ to C₃₀ diaryl ether; alternatively, a C₂ to C₃₀ aliphaticacyclic ether; alternatively, a C₃ to C₃₀ aliphatic cyclic ether;alternatively, a C₄ to C₃₀ aromatic cyclic ether; or alternatively, aC₁₂ to C₃₀ diaryl ether. In other embodiments, each neutral ligandindependently can be a C₂ to C₂₀ aliphatic acyclic ether, a C₃ to C₂₀aliphatic cyclic ether, a C₄ to C₂₀ aromatic cyclic ether, or a C₁₂ toC₂₀ diaryl ether; alternatively, a C₂ to C₂₀ aliphatic acyclic ether;alternatively, a C₃ to C₂₀ aliphatic cyclic ether; alternatively, a C₄to C₂₀ aromatic cyclic ether; or alternatively, a C₁₂ to C₂₀ diarylether.

In an embodiment, the aliphatic acyclic ether can be dimethyl ether,diethyl ether, a dipropyl ether, a dibutyl ether, methyl ethyl ether, amethyl propyl ether, a methyl butyl ether, or any combination thereof.In some embodiments, the aliphatic acyclic ether can be dimethyl ether;alternatively, diethyl ether; alternatively, a dipropyl ether;alternatively, a dibutyl ether; alternatively, methyl ethyl ether;alternatively, a methyl propyl ether; or alternatively, a methyl butylether.

In an embodiment, the aliphatic cyclic ether can be tetrahydrofuran, asubstituted tetrahydrofuran, a dihydrofuran, a substituted dihydrofuran,1,3-dioxolane, a substituted 1,3-dioxolane, tetrahydropyran, asubstituted tetrahydropyran, a dihydropyran, a substituted dihydropyran,pyran, a substituted pyran, a dioxane, or a substituted dioxane;alternatively, tetrahydrofuran or a substituted tetrahydrofuran;alternatively, a dihydrofuran or a substituted dihydrofuran;alternatively, 1,3-dioxolane or a substituted 1,3-dioxolane;alternatively, tetrahydropyran or a substituted tetrahydropyran;alternatively, a dihydropyran or a substituted dihydropyran;alternatively, pyran or a substituted pyran; or alternatively, a dioxaneor a substituted dioxane. In some embodiments, the aliphatic cyclicether can be tetrahydrofuran, tetrahydropyran, or dioxane, or anycombination thereof; alternatively, tetrahydrofuran, alternativelytetrahydropyran; or alternatively, dioxane. Substituents (general andspecific) are independently disclosed herein and can be utilized withoutlimitation to further describe a substituted tetrahydrofuran,dihydrofuran, 1,3-dioxolane, tetrahydrofuran, tetrahydropyran, pyran ordioxane which can be utilized as the neutral ligand.

In an embodiment, the aromatic cyclic ether can be furan, a substitutedfuran, benzofuran, a substituted benzofuran, isobenzofuran, asubstituted isobenzofuran, dibenzofuran, a substituted dibenzofuran, orany combination thereof; alternatively, furan or a substituted furan;alternatively, benzofuran or a substituted benzofuran; alternatively,isobenzofuran or a substituted isobenzofuran; or alternatively, adibenzofuran or a substituted dibenzofuran. In some embodiments, thearomatic cyclic ether can be furan, benzofuran, isobenzofuran,dibenzofuran, or any combination thereof; alternatively, furan;alternatively, benzofuran; alternatively, isobenzofuran; oralternatively, dibenzofuran. In an embodiment, the diaryl ether can bediphenyl ether, a substituted diphenyl ether, ditolyl ether, asubstituted ditolyl ether, or any combination thereof; alternatively,diphenyl ether or a substituted diphenyl ether; or alternatively,ditolyl ether or a substituted ditolyl ether. In some embodiments, thediaryl ether can be diphenyl ether or ditolyl ether; alternatively,diphenyl ether; or ditolyl ether. Substituents (general and specific)are independently disclosed herein and can be utilized withoutlimitation to further describe a substituted furan, benzofuran, ordibenzofuran which can be utilized as the neutral ligand.

The features of the transition metal salts have been independentlydescribed herein and can be utilized in any combination to describe thetransition metal salt of the N²-phosphinyl formamidine metal saltcomplex comprising a transition metal salt complexed to an N²-phosphinylformamidine compound.

In a non-limiting embodiment, the transition metal salt which can beutilized includes chromium(II) halides, chromium(III) halides,chromium(II) carboxylates, chromium(III) carboxylates, chromium(II)β-diketonates, chromium(III) β-diketonates, chromium(II) halide (THF)complexes, chromium(III) halide (THF) complexes, iron(II) halides,iron(III) halides, iron(II) carboxylates, iron(III) carboxylates,iron(II) β-diketonates, iron(III) β-diketonates, cobalt(II) halides,cobalt(III) halides, cobalt(II) carboxylates, cobalt(III) carboxylates,cobalt(II) β-diketonates, cobalt(III) β-diketonates, nickel(II) halides,nickel(II) carboxylates, nickel(II) β-diketonates, palladium(II)halides, palladium(II) carboxylates, palladium(II) β-diketonates,platinum(II) halides, platinum(IV) halides, platinum(II) carboxylates,or platinum(IV) carboxylates. In some non-limiting embodiments, thetransition metal salt can be a chromium(II) halide, a chromium(III)halide, a chromium (II) carboxylate, a chromium(III) carboxylate, achromium(II) β-diketonate, a chromium(III) β-diketonate, a chromium(II)halide (THF) complex, or a chromium(III) halide (THF) complex;alternatively, an iron(II) halide, an iron(III) halide, an iron(II)carboxylate, an iron(III) carboxylate, an iron(II) β-diketonate, or aniron(III) β-diketonate; alternatively, a cobalt(II) halide, acobalt(III) halide, a cobalt(II) carboxylate, a cobalt(III) carboxylate,a cobalt(II) β-diketonate, or a cobalt(III) β-diketonate; alternatively,a nickel(II) halide, a nickel(II) carboxylate, or a nickel(II)β-diketonate; alternatively, a palladium(II) halide, a palladium(II)carboxylate, or a palladium(II) β-diketonate; or alternatively, aplatinum(II) halide, a platinum(IV) halide, a platinum(II) carboxylate,or a platinum(IV) carboxylate. In some embodiments, the transition metalsalt can be a chromium(III) halide, a chromium(III) carboxylate, achromium(III) β-diketonate, a chromium(III) halide (THF) complex;alternatively, an iron(III) halide, an iron(III) carboxylate, or aniron(III) β-diketonate; or alternatively, a cobalt(III) halide, acobalt(III) carboxylate, or a cobalt(III) β-diketonate. In otherembodiments, the transition metal salt can be a be a chromium(II)halide; alternatively, a chromium(III) halide; alternatively, a chromium(II) carboxylate; alternatively, a chromium(III) carboxylate;alternatively, a chromium(II) β-diketonate; alternatively, achromium(III) β-diketonate; alternatively, a chromium(II) halide (THF)complex; alternatively, a chromium(III) halide (THF) complex;alternatively, an iron(II) halide; alternatively, an iron(III) halide;alternatively, an iron(II) carboxylate; alternatively, an iron(III)carboxylate; alternatively, an iron(II) β-diketonate; alternatively, aniron(III) β-diketonate; alternatively, a cobalt(II) halide;alternatively, a cobalt(III) halide; alternatively, a cobalt(II)carboxylate; alternatively, a cobalt(III) carboxylate; alternatively, acobalt(II) β-diketonate; alternatively, a cobalt(III) β-diketonate;alternatively, a nickel(II) halide; alternatively, a nickel(II)carboxylate; alternatively, a nickel(II) β-diketonate; alternatively, apalladium(II) halide; alternatively, a palladium(II) carboxylate;alternatively, a palladium(II) β-diketonate; alternatively, aplatinum(II) halide; alternatively, a platinum(IV) halide;alternatively, a platinum(II) carboxylate; or alternatively, aplatinum(IV) carboxylate.

In some non-limiting embodiments, transition metal salts which can beutilized includes chromium(II) chloride, chromium(III) chloride,chromium(II) fluoride, chromium(III) fluoride, chromium(II) bromide,chromium(III) bromide, chromium(II) iodide, chromium(III) iodide,chromium(III) chloride (THF) complex, chromium(II) acetate,chromium(III) acetate, chromium(II) 2-ethylhexanoate, chromium(III)2-ethylhexanoate, chromium(II) triflate, chromium(III) triflate,chromium(III) nitrate, chromium(III) acetylacetonate, chromium(III)hexafluoracetylacetonate, chromium(III) benzoylacetonate, iron(II)chloride, iron(III) chloride, iron(II) fluoride, iron(III) fluoride,iron(II) bromide, iron(III) bromide, iron(II) iodide, iron(III) iodide,iron(II) acetate, iron(III) acetate, iron(II) acetylacetonate, iron(III)acetylacetonate, iron(II) 2-ethylhexanoate, iron(III) 2-ethylhexanoate,iron(II) triflate, iron(III) triflate, iron(III) nitrate, cobalt(II)chloride, cobalt(III) chloride, cobalt(II) fluoride, cobalt(III)fluoride, cobalt(II) bromide, cobalt(III) bromide, cobalt(II) iodide,cobalt(III) iodide, cobalt(II) acetate, cobalt(III) acetate, cobalt(II)acetylacetonate, cobalt(III) acetylacetonate, cobalt(II)2-ethylhexanoate, cobalt(III) 2-ethylhexanoate, cobalt(II) triflate,cobalt(III) triflate, cobalt(III) nitrate, nickel(II) chloride,nickel(II) fluoride, nickel(II) bromide, nickel(II) iodide, nickel(II)acetate, nickel(II) 2-ethylhexanoate, nickel(II) triflate, nickel(II)nitrate, nickel(II) acetylacetonate, nickel(II) benzoylacetonate,nickel(II) hexafluoracetylacetonate, palladium(II) chloride,palladium(II) fluoride, palladium(II) bromide, palladium(II) iodide,palladium(II) acetate, palladium(II) acetylacetonate, palladium(II)nitrate, platinum(II) chloride, platinum(II) bromide, platinum(II)iodide, or platinum(IV) chloride. In other embodiments, the transitionmetal salt can be chromium(II) chloride, chromium(III) chloride,chromium(II) fluoride, chromium(III) fluoride, chromium(II) bromide,chromium(III) bromide, chromium(II) iodide, chromium(III) iodide,chromium(III) chloride (THF) complex, chromium(II) acetate,chromium(III) acetate, chromium(II) 2-ethylhexanoate, chromium(III)2-ethylhexanoate chromium(II) triflate, chromium(III) triflate,chromium(III) nitrate, chromium(III) acetylacetonate, chromium(III)hexafluoracetylacetonate, or chromium(III) benzoylacetonate;alternatively, iron(II) chloride, iron(III) chloride, iron(II) fluoride,iron(III) fluoride, iron(II) bromide, iron(III) bromide, iron(II)iodide, iron(III) iodide, iron(II) acetate, iron(III) acetate, iron(II)acetylacetonate, iron(III) acetylacetonate, iron(II) 2-ethylhexanoate,iron(III) 2-ethylhexanoate, iron(II) triflate, iron(III) triflate, oriron(III) nitrate; alternatively, cobalt(II) chloride, cobalt(III)chloride, cobalt(II) fluoride, cobalt(III) fluoride, cobalt(II) bromide,cobalt(III) bromide, cobalt(II) iodide, cobalt(III) iodide, cobalt(II)acetate, cobalt(III) acetate, cobalt(II) acetylacetonate, cobalt(III)acetylacetonate, cobalt(II) 2-ethylhexanoate, cobalt(III)2-ethylhexanoate, cobalt(II) triflate, cobalt(III) triflate, orcobalt(III) nitrate; alternatively, nickel(II) chloride, nickel(II)fluoride, nickel(II) bromide, nickel(II) iodide, nickel(II) acetate,nickel(II) 2-ethylhexanoate, nickel(II) triflate, nickel(II) nitrate,nickel(II) acetylacetonate, nickel(II) benzoylacetonate, or nickel(II)hexafluoracetylacetonate; alternatively, palladium(II) chloride,palladium(II) fluoride, palladium(II) bromide, palladium(II) iodide,palladium(II) acetate, palladium(II) acetylacetonate, or palladium(II)nitrate; or alternatively, platinum(II) chloride, platinum(II) bromide,platinum(II) iodide, or platinum(IV) chloride. In yet other embodiments,the transition metal salt can be chromium(III) chloride, chromium(III)fluoride, chromium(III) bromide, chromium(III) iodide, chromium(III)chloride (THF) complex, chromium(III) acetate, chromium(III)2-ethylhexanoate, chromium(III) triflate, chromium(III) nitrate,chromium(III) acetylacetonate, chromium(III) hexafluoracetylacetonate,or chromium(III) benzoylacetonate; or alternatively, iron(III) chloride,iron(III) fluoride, iron(III) bromide, iron(III) iodide, iron(III)acetate, iron(III) acetylacetonate, iron(III) 2-ethylhexanoate,iron(III) triflate, or iron(III) nitrate. In further embodiments, thetransition metal salt can be chromium(III) chloride, chromium(III)chloride (THF) complex, or chromium(III) acetylacetonate; oralternatively, iron(III) chloride, or iron(III) acetylacetonate.

In some non-limiting embodiments, transition metal salts which can beutilized includes chromium(II) chloride; alternatively, chromium(III)chloride; alternatively, chromium(II) fluoride; alternatively,chromium(III) fluoride; alternatively, chromium(II) bromide;alternatively, chromium(III) bromide; alternatively, chromium(II)iodide; alternatively, chromium(III) iodide; alternatively,chromium(III) chloride (THF) complex; alternatively, chromium(II)acetate; alternatively, chromium(III) acetate; alternatively,chromium(II) 2-ethylhexanoate; alternatively, chromium(III)2-ethylhexanoate; alternatively, chromium(II) triflate; alternatively,chromium(III) triflate; alternatively, chromium(III) nitrate;alternatively, chromium(III) acetylacetonate; alternatively,chromium(III) hexafluoracetylacetonate; alternatively, chromium(III)benzoylacetonate; alternatively, iron(II) chloride; alternatively,iron(III) chloride; alternatively, iron(II) fluoride; alternatively,iron(III) fluoride; alternatively, iron(II) bromide; alternatively,iron(III) bromide; alternatively, iron(II) iodide; alternatively,iron(III) iodide; alternatively, iron(II) acetate; alternatively,iron(III) acetate; alternatively, iron(II) acetylacetonate;alternatively, iron(III) acetylacetonate; alternatively, iron(II)2-ethylhexanoate; alternatively, iron(III) 2-ethylhexanoate;alternatively, iron(II) triflate; alternatively, iron(III) triflate;alternatively, iron(III) nitrate; alternatively, cobalt(II) chloride;alternatively, cobalt(III) chloride; alternatively, cobalt(II) fluoride;alternatively, cobalt(III) fluoride; alternatively, cobalt(II) bromide;alternatively, cobalt(III) bromide; alternatively, cobalt(II) iodide;alternatively, cobalt(III) iodide; alternatively, cobalt(II) acetate;alternatively, cobalt(III) acetate; alternatively, cobalt(II)acetylacetonate; alternatively, cobalt(III) acetylacetonate;alternatively, cobalt(II) 2-ethylhexanoate; alternatively, cobalt(III)2-ethylhexanoate; alternatively, cobalt(II) triflate; alternatively,cobalt(III) triflate; alternatively, cobalt(III) nitrate; alternatively,nickel(II) chloride; alternatively, nickel(II) fluoride; alternatively,nickel(II) bromide; alternatively, nickel(II) iodide; alternatively,nickel(II) acetate; alternatively, nickel(II) 2-ethylhexanoate;alternatively, nickel(II) triflate; alternatively, nickel(II) nitrate;alternatively, nickel(II) acetylacetonate; alternatively, nickel(II)benzoylacetonate; alternatively, nickel(II) hexafluoracetylacetonate;alternatively, palladium(II) chloride; alternatively, palladium(II)fluoride; alternatively, palladium(II) bromide; alternatively,palladium(II) iodide; alternatively, palladium(II) acetate;alternatively, palladium(II) acetylacetonate; alternatively,palladium(II) nitrate; alternatively, platinum(II) chloride;alternatively, platinum(II) bromide; alternatively, platinum(II) iodide;or alternatively, platinum(IV) chloride.

In a non-limiting embodiment, the transition metal salt which can beutilized includes a chromium(II) dicarboxylate, chromium(III)dicarboxylate, iron(II) dicarboxylate, iron(III) dicarboxylate,cobalt(II) dicarboxylate, cobalt(III) dicarboxylate, nickel(II)dicarboxylate, palladium(II) dicarboxylate, or platinum(II) carboxylate;alternatively, a chromium(II) dicarboxylate or chromium(III)dicarboxylate; alternatively, an iron(II) dicarboxylate or an iron(III)dicarboxylate; alternatively, a cobalt(II) dicarboxylate or cobalt(III)dicarboxylate; alternatively, a chromium(II) dicarboxylate;alternatively, a chromium(III) dicarboxylate; alternatively, an iron(II)dicarboxylate; alternatively, an iron(III) dicarboxylate; alternatively,a cobalt(II) dicarboxylate; alternatively, a cobalt(III) dicarboxylate;alternatively, a nickel(II) dicarboxylate; alternatively, apalladium(II) dicarboxylate; or alternatively, a platinum(II)carboxylates. Dicarboxylate dianionic ligands are described herein andthese dicarboxylate dianionic ligands can be utilized without limitationto further name the transition metal salts which can be utilized as thetransition metal salt.

It should be appreciated, that a given N²-phosphinyl formamidine metalsalt complex can have one or more neutral ligands even when the metalsalt utilized to produce the N²-phosphinyl formamidine metal saltcomplex did not have any neutral ligands.

Catalyst Systems

In an aspect, the present disclosure relates to catalyst systemscomprising an N²-phosphinyl formamidine compound and a metal salt;alternatively, an N²-phosphinyl formamidine metal salt complex. In anembodiment, the catalyst system can comprise, or consist essentially of,an N²-phosphinyl formamidine metal salt complex and a metal alkyl; oralternatively, an N²-phosphinyl formamidine metal salt complex and analuminoxane. In another aspect, the catalyst system can comprise, orconsist essentially of, an N²-phosphinyl formamidine compound, a metalsalt, and a metal alkyl; or alternatively, an N²-phosphinyl formamidinecompound, a metal salt, and an aluminoxane. The N²-phosphinylformamidine metal salt complex, metal salt, N²-phosphinyl formamidinecompound, metal alkyl, and aluminoxane which can be utilized in variousaspects and/or embodiments of the catalyst system are independentlydescribed herein and can be utilized in any combination and withoutlimitation to describe various catalyst systems of this disclosure.

The N²-phosphinyl formamidine metal salt complex(es) and metal alkylswhich can be utilized in various catalyst systems of this disclosure cancomprise a metal salt complexed to an N²-phosphinyl formamidinecompound. The N²-phosphinyl formamidine metal salt complexes, metalsalts, and N²-phosphinyl formamidine compounds are independentlydescribed herein and can be utilized without limitation to describe anN²-phosphinyl formamidine metal salt complex which can be utilized invarious catalyst systems of this disclosure.

Metal Alkyl

Generally, the metal alkyl compound which can be utilized in thecatalyst system of this disclosure can be any heteroleptic or homolepticmetal alkyl compound. In an embodiment, the metal alkyl can comprise,consist essentially of, or consist of, a non-halide metal alkyl, a metalalkyl halide, or any combination thereof; alternatively a non-halidemetal alkyl; or alternatively, a metal alkyl halide.

In an embodiment, the metal of the metal alkyl can comprise, consistessentially of, or consist of, a group 1, 2, 11, 12, 13, or 14 metal; oralternatively a group 13 or 14 metal; or alternatively, a group 13metal. In some embodiments, the metal of the metal alkyl (non-halidemetal alkyl or metal alkyl halide) can be lithium, sodium, potassium,rubidium, cesium, beryllium, magnesium, calcium, strontium, barium,zinc, cadmium, boron, aluminum, or tin; alternatively, lithium, sodium,potassium, magnesium, calcium, zinc, boron, aluminum, or tin;alternatively, lithium, sodium, or potassium; alternatively magnesium,calcium; alternatively, lithium; alternatively, sodium; alternatively,potassium; alternatively, magnesium; alternatively, calcium;alternatively, zinc; alternatively, boron; alternatively, aluminum; oralternatively, tin. In some embodiments, the metal alkyl (non-halidemetal alkyl or metal alkyl halide) can comprise, consist essentially of,or consist of, a lithium alkyl, a sodium alkyl, a magnesium alkyl, aboron alkyl, a zinc alkyl, or an aluminum alkyl. In some embodiments,the metal alkyl (non-halide metal alkyl or metal alkyl halide) cancomprise, consist essentially of, or consist of, an aluminum alkyl.

In an embodiment, the aluminum alkyl can be a trialkylaluminum, analkylaluminum halide, an alkylaluminum alkoxide, an aluminoxane, or anycombination thereof. In some embodiments, the aluminum alkyl can be atrialkylaluminum, an alkylaluminum halide, an aluminoxane, or anycombination thereof; or alternatively, a trialkylaluminum, analuminoxane, or any combination thereof. In other embodiments, thealuminum alkyl can be a trialkylaluminum; alternatively, analkylaluminum halide; alternatively, an alkylaluminum alkoxide; oralternatively, an aluminoxane.

In a non-limiting embodiment, the aluminoxane can have a repeating unitcharacterized by the Formula I:

wherein R′ is a linear or branched alkyl group. Alkyl groups for metalalkyls have been independently described herein and can be utilizedwithout limitation to further describe the aluminoxanes having FormulaI. Generally, n of Formula I is greater than 1; or alternatively greaterthan 2. In an embodiment, n can range from 2 to 15; or alternatively,range from 3 to 10.

In an aspect, each halide of any metal alkyl halide disclosed herein canindependently be fluoride, chloride, bromide, or iodide; alternatively,chloride, bromide, or iodide. In an embodiment, each halide of any metalalkyl halide disclosed herein can be fluoride; alternatively, chloride;alternatively, bromide; or alternatively, iodide.

In an aspect, each alkyl group of any metal alkyl disclosed herein(non-halide metal alkyl or metal alkyl halide) independently can be a C₁to C₂₀ alkyl group; alternatively, a C₁ to C₁₀ alkyl group; oralternatively, a C₁ to C₆ alkyl group. In an embodiment, each alkylgroup(s) independently can be a methyl group, an ethyl group, a propylgroup, a butyl group, a pentyl group, a hexyl group, a heptyl group, oran octyl group; alternatively, a methyl group, an ethyl group, a butylgroup, a hexyl group, or an octyl group. In some embodiments, each alkylgroup independently can be a methyl group, an ethyl group, an n-propylgroup, a n-butyl group, an iso-butyl group, an n-hexyl group, or ann-octyl group; alternatively, a methyl group, an ethyl group, an n-butylgroup, or an iso-butyl group; alternatively, a methyl group;alternatively, an ethyl group; alternatively, an n-propyl group;alternatively, an n-butyl group; alternatively, an iso-butyl group;alternatively, an n-hexyl group; or alternatively, an n-octyl group.

In an aspect, the alkoxide group of any metal alkyl alkoxide disclosedherein independently can be a C₁ to C₂₀ alkoxy group; alternatively, aC₁ to C₁₀ alkoxy group; or alternatively, a C₁ to C₆ alkoxy group. In anembodiment, each alkoxide group of any metal alkyl alkoxide disclosedherein independently can be a methoxy group, an ethoxy group, a propoxygroup, a butoxy group, a pentoxy group, a hexoxy group, a heptoxy group,or an octoxy group; alternatively, a methoxy group, an ethoxy group, abutoxy group, a hexoxy group, or an octoxy group. In some embodiments,each alkoxide group of any metal alkyl alkoxide disclosed hereinindependently can be a methoxy group, an ethoxy group, an n-propoxygroup, an n-butoxy group, an iso-butoxy group, an n-hexoxy group, or ann-octoxy group; alternatively, a methoxy group, an ethoxy group, ann-butoxy group, or an iso-butoxy group; alternatively, a methoxy group;alternatively, an ethoxy group; alternatively, an n-propoxy group;alternatively, an n-butoxy group; alternatively, an iso-butoxy group;alternatively, an n-hexoxy group; or alternatively, an n-octoxy group.

In a non-limiting embodiment, useful metal alkyls can include methyllithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, diethylmagnesium, di-n-butylmagnesium, ethylmagnesium chloride,n-butylmagnesium chloride, and diethyl zinc. In a non-limitingembodiment, useful trialkylaluminum compounds can includetrimethylaluminum, triethylaluminum, tripropylaluminum,tributylaluminum, trihexylaluminum, trioctylaluminum, or mixturesthereof. In some non-limiting embodiments, trialkylaluminum compoundscan include trimethylaluminum, triethylaluminum, tripropylaluminum,tri-n-butylaluminum, tri-isobutylaluminum, trihexylaluminum,tri-n-octylaluminum, or mixtures thereof; alternatively,triethylaluminum, tri-n-butylaluminum, tri-isobutylaluminum,trihexylaluminum, tri-n-octylaluminum, or mixtures thereof;alternatively, triethylaluminum, tri-n-butylaluminum, trihexylaluminum,tri-n-octylaluminum, or mixtures thereof. In other non-limitingembodiments, useful trialkylaluminum compounds can includetrimethylaluminum; alternatively, triethylaluminum; alternatively,tripropylaluminum; alternatively, tri-n-butylaluminum; alternatively,tri-isobutylaluminum; alternatively, trihexylaluminum; or alternatively,tri-n-octylaluminum.

In a non-limiting embodiment, useful alkylaluminum halides can includediethylaluminum chloride, diethylaluminum bromide, ethylaluminumdichloride, ethylaluminum sesquichloride, and mixtures thereof. In somenon-limiting embodiments, useful alkylaluminum halides can includediethylaluminum chloride, ethylaluminum dichloride, ethylaluminumsesquichloride, and mixtures thereof. In other non-limiting embodiments,useful alkylaluminum halides can include diethylaluminum chloride;alternatively, diethylaluminum bromide; alternatively, ethylaluminumdichloride; or alternatively, ethylaluminum sesquichloride.

In a non-limiting embodiment, useful aluminoxanes can includemethylaluminoxane (MAO), ethylaluminoxane, modified methylaluminoxane(MMAO), n-propylaluminoxane, iso-propylaluminoxane, n-butylaluminoxane,sec-butylaluminoxane, iso-butylaluminoxane, t-butyl aluminoxane,1-pentylaluminoxane, 2-pentylaluminoxane, 3-pentylaluminoxane,iso-pentylaluminoxane, neopentylaluminoxane, or mixtures thereof. Insome non-limiting embodiments, useful aluminoxanes can includemethylaluminoxane (MAO), modified methylaluminoxane (MMAO), isobutylaluminoxane, t-butyl aluminoxane, or mixtures thereof. In othernon-limiting embodiments, useful aluminoxanes can includemethylaluminoxane (MAO); alternatively, ethylaluminoxane; alternatively,modified methylaluminoxane (MMAO); alternatively, n-propylaluminoxane;alternatively, iso-propylaluminoxane; alternatively, n-butylaluminoxane;alternatively, sec-butylaluminoxane; alternatively,iso-butylaluminoxane; alternatively, t-butyl aluminoxane; alternatively,1-pentylaluminoxane; alternatively, 2-pentylaluminoxane; alternatively,3-pentylaluminoxane; alternatively, iso-pentylaluminoxane; oralternatively, neopentylaluminoxane.

Catalyst System Component Ratios

In an aspect, the metal alkyl and N²-phosphinyl formamidine metal saltcomplex can be combined in any ratio that forms an active catalystsystem. In an embodiment, the metal of the metal alkyl to the metal ofthe N²-phosphinyl formamidine metal salt complex molar ratio can begreater than or equal to 5:1; alternatively, greater than or equal to10:1; alternatively, greater than or equal to 25:1; alternatively,greater than or equal to 50:1; or alternatively, greater than or equalto 100:1. In some embodiments, the metal of the metal alkyl to the metalof the N²-phosphinyl formamidine metal salt complex molar ratio canrange from 5:1 to 100,000:1; alternatively, range from 10:1 to 50,000:1;alternatively, range from 25:1 to 10,000:1; alternatively, range from50:1 to 5,000:1; or alternatively, range from 100:1 to 2,500:1. When ametal alkyl having a specific metal and an N²-phosphinyl formamidinemetal salt complex having a specific metal is utilized the metal of themetal alkyl to the metal of the N²-phosphinyl formamidine metal saltcomplex molar ratio can be stated as a specific metal of the metal alkylto specific metal of the N²-phosphinyl formamidine metal salt complexmolar ratio. For example, when the metal alkyl is an alkylaluminumcompound (e.g. trialkylaluminum, alkylaluminum halide, alkylaluminumalkoxide, and/or aluminoxane) and the N²-phosphinyl formamidine metalsalt complex is an N²-phosphinyl formamidine chromium salt complex, themetal of the metal alkyl to metal of the metal salt can be an aluminumto chromium molar ratio. In some non-limiting embodiments, the aluminumto chromium molar ratio can be greater than or equal to 5:1;alternatively, greater than or equal to 10:1; alternatively, greaterthan or equal to 25:1; alternatively, greater than or equal to 50:1;alternatively, greater than or equal to 100:1; alternatively, range from5:1 to 100,000:1; alternatively, range from 10:1 to 50,000:1;alternatively, range from 25:1 to 10,000:1; alternatively, range from50:1 to 5,000:1; or alternatively, range from 100:1 to 2,500:1.

In another aspect, the metal alkyl, metal salt, and N²-phosphinylformamidine compound can be combined in any ratio that forms an activecatalyst system. Generally the ratio of the components of the catalystsystem comprising, consisting essentially of, or consisting of a metalalkyl, metal salt, and N²-phosphinyl formamidine compound can beprovided as a molar ratio of the metal of the metal alkyl to metal ofthe metal salt and an equivalent ratio of the N²-phosphinyl formamidinecompound to metal salt.

In an embodiment, the metal of the metal alkyl to the metal of the metalsalt molar ratio can be greater than or equal to 5:1; alternatively,greater than or equal to 10:1; alternatively, greater than or equal to25:1; alternatively, greater than or equal to 50:1; or alternatively,greater than or equal to 100:1. In some embodiments, the metal of themetal alkyl to the metal of the metal salt molar ratio can range from5:1 to 100,000:1; alternatively, ranges from 10:1 to 50,000:1;alternatively, ranges from 25:1 to 10,000:1; alternatively, ranges from50:1 to 5,000:1; or alternatively, ranges from 100:1 to 2,500:1. When ametal alkyl having a specific metal and a metal salt having a specificmetal is utilized the metal of the metal alkyl to the metal of the metalsalt molar ratio can be stated as a specific metal of the metal alkyl tospecific metal of the metal salt molar ratio. For example, when themetal alkyl is an alkylaluminum compound (e.g. trialkylaluminum,alkylaluminum halide, alkylaluminum alkoxide, and/or aluminoxane) andthe metal salt is a chromium salt, the metal of the metal alkyl to metalof the metal salt can be an aluminum to chromium molar ratio. In somenon-limiting embodiments, the aluminum to chromium molar ratio can begreater than or equal to 5:1; alternatively, greater than or equal to10:1; alternatively, greater than or equal to 25:1; alternatively,greater than or equal to 50:1; alternatively, greater than or equal to100:1; alternatively, range from 5:1 to 100,000:1; alternatively, rangefrom 10:1 to 50,000:1; alternatively, range from 25:1 to 10,000:1;alternatively, range from 50:1 to 5,000:1; or alternatively, range from100:1 to 2,500:1

In an embodiment, the N²-phosphinyl formamidine compound to metal saltequivalent ratio can be greater than or equal to 0.8:1; alternatively,greater than or equal to 0.9:1; or alternatively, greater than or equalto 0.95:1; or alternatively, greater than or equal to 0.98:1. In someembodiments, the N²-phosphinyl formamidine compound to metal saltequivalent ratio can be range from 0.8:1 to 5:1; alternatively, rangefrom 0.9:1 to 4:1; or alternatively, range from 0.95:1 to 3:1; oralternatively, range from 0.98:1 to 2.5:1. In other embodiments, theN²-phosphinyl formamidine compound to metal salt equivalent ratio can beabout 1:1.

Methods of Preparing an N²-Phosphinyl Formamidine Compound andN²-Phosphinyl Formamidine Compound Metal Salt Complex

In an aspect, this disclosure relates to a method of preparing anN²-phosphinyl formamidine compound and/or an N²-phosphinyl formamidinemetal salt complex. N²-phosphinyl formamidine compounds andN²-phosphinyl formamidine metal salt complexes are generally describedherein and methods of preparing them can be generally applied to anyN²-phosphinyl formamidine compound and/or N²-phosphinyl formamidinemetal salt complex described herein.

Method of Preparing an N²-Phosphinyl Formamidine Compound

In an aspect, this disclosure relates to a method of preparing anN²-phosphinyl formamidine compound. Generally, the method of preparingan N²-phosphinyl formamidine compound can comprise: a) contacting aphosphine halide with a metal formamidinate, and b) forming theN²-phosphinyl formamidinate. Generally, the N²-phosphinyl formamidinecompound can be formed under conditions capable of forming anN²-phosphinyl formamidine group. In some embodiments, the N²-phosphinylformamidine compound can be isolated; alternatively, purified; oralternatively, isolated and purified. General and specific phosphinehalides and metal formamidinate are disclosed herein and can beutilized, without limitation, to further describe the method to preparethe N²-phosphinyl formamidine compound.

In an embodiment, the N²-phosphinyl formamidine compound can have anyStructure described herein. In some embodiments, the N²-phosphinylformamidine compound may not have an N² hydrogen atom (e.g., theN²-phosphinyl formamidine compound Structures NPF1, NPF2, and/or NPF4where R³ is a non-hydrogen group). In other embodiments, theN²-phosphinyl formamidine compound can have an N² hydrogen atom (e.g.,the N²-phosphinyl formamidine compound Structures NPF6, NPF7, and/orNPF9).

Generally, the metal formamidinate utilized in the method of preparingthe N²-phosphinyl formamidine compound can have Structure MFA1 or MFA2;alternatively, Structure MFA1; or alternatively, Structure MFA2.

Generally, the metal formamidinate structures prefaced with thedesignation MFA correspond with the N²-phosphinyl formamidine structuresprefaced with the designation NPF having the same number designation. R¹and R³ within metal formamidine Structures MFA1 and/or MFA2 and/or areindependently described as features of the N²-phosphinyl formamidinecompound having Structures NPF1 and/or NPF2. Since metal formamidinateStructures MFA1 and/or MFA2 are utilized to prepare embodiments ofN²-phosphinyl formamidine compounds having Structures NPF1 and/or NPF2,the R¹ and R³ descriptions for the N²-phosphinyl formamidine compoundscan be utilized without limitation to further describe metalformamidinate Structures MFA1 and/or MFA2.

Within this disclosure, phosphine halides can be used to ultimatelyprepare the N²-phosphinyl formamidine compounds and/or the N²-phosphinylformamidine metal salt complexes utilized in various aspects of thisdisclosure. In various embodiments, phosphine halides which can beutilized have Structure PH1.

R⁴ and R⁵ are described as features of N²-phosphinyl formamidinecompounds having Structures NPF1, NPF2, NPF4, NPF6, NPF7, and/or NPF9and are described herein. Additionally, X¹ is described herein as afeature of the phosphine halides. Since the phosphine halides areutilized to ultimately prepare embodiments of the N²-phospinylformamidine compounds having Structures NPF1, NPF2, NPF4, NPF6, NPF7,and/or NPF9, X¹, R⁴, and R⁵ can utilized without limitation to furtherdescribe the phosphine halides having StructurePH1. In an embodiment, X¹of the phosphine halide can be fluoro, chloro, bromo, or iodo;alternatively, fluoro; alternatively, chloro; alternatively, bromo; oralternatively, iodo.

In an aspect, the phosphine halide can be a diphenylphosphine halide, adialkylphosphine halide, a bis(mono-halo substituted phenyl)phosphinehalide, a bis(mono-alkyl substituted phenyl)phosphine halide, or abis(mono-alkoxy substituted phenyl)phosphine halide; alternatively, adiphenylphosphine halide; alternatively, a dialkylphosphine halide;alternatively, a bis(mono-halo substituted phenyl)phosphine halide;alternatively, a bis(mono-alkyl substituted phenyl)phosphine halide; oralternatively, a bis(mono-alkoxy substituted phenyl)phosphine halide. Inanother aspect, phosphine halide can be an (alkyl)(phenyl)phosphinehalide, a (mono-halo substituted phenyl)(phenyl)phosphine halide, a(mono-alkyl substituted phenyl)(phenyl)phosphine halide, a (mono-alkoxysubstituted phenyl)(phenyl)phosphine halide, a (mono-alkyl substitutedphenyl)(mono-halo substituted phenyl) phosphine halide, or a (mono-alkylsubstituted phenyl)(mono-alkoxy substituted phenyl) phosphine halide;alternatively, (alkyl)(phenyl)phosphine halide; alternatively, a(mono-halo substituted phenyl)(phenyl)phosphine halide; alternatively, a(mono-alkyl substituted phenyl)(phenyl)phosphine halide; alternatively,a (mono-alkoxy substituted phenyl)(phenyl)phosphine halide;alternatively, a (mono-alkyl substituted phenyl)(mono-halo substitutedphenyl) phosphine halide; or alternatively, a (mono-alkyl substitutedphenyl)(mono-alkoxy substituted phenyl) phosphine halide. In anotheraspect, phosphine halide can be a bis(dihalo substitutedphenyl)phosphine halide, a bis(dialkyl substituted phenyl)phosphinehalide, a bis(dialkoxy substituted phenyl)phosphine halide, abis(trialkylphenyl)phosphine halide, or a bis(trialkoxyphenyl)phosphinehalide; alternatively, a bis(dihalo substituted phenyl)phosphine halide;alternatively, a bis(dialkyl substituted phenyl)phosphine halide;alternatively, a bis(dialkoxy substituted phenyl)phosphine halide;alternatively, a bis(trialkylphenyl)phosphine halide; or alternatively,a bis(trialkoxyphenyl)phosphine halide. Halo, alkyl, and alkoxysubstituents for the substituted phenyl group embodiments of thephosphine halides have been disclosed herein and can be utilized,without limitation to further describe the phosphine halides which canbe utilized in aspects and embodiments described herein.

In a non-limiting aspect, the phosphine halide can be dimethylphosphinechloride, diethylphosphine chloride, diisopropylphosphine chloride,di-tert-butylphosphine chloride, or di-neo-pentylphosphine chloride;alternatively, dimethylphosphine chloride, diethylphosphine chloride,di-n-propylphosphine chloride, di-n-butylphosphine chloride,di-n-pentylphosphine chloride, or di-n-hexylphosphine chloride. In anembodiment, the phosphine halide can be dimethylphosphine chloride;alternatively, diethylphosphine chloride; alternatively,di-n-propylphosphine chloride; alternatively, diisopropylphosphinechloride; alternatively, di-n-butylphosphine chloride; alternatively,di-tert-butylphosphine chloride; alternatively, di-n-pentylphosphinechloride; alternatively, di-neo-pentylphosphine chloride; oralternatively, di-n-hexylphosphine chloride.

In a non-limiting aspect, the phosphine halide can be(methyl)(phenyl)phosphine chloride, (ethyl)(phenyl)phosphine chloride,(isopropyl)(phenyl)phosphine chloride, (tert-butyl)(phenyl)phosphinechloride, or (neo-pentyl)(phenyl)phosphine chloride. In an embodiment,the phosphine halide can be (methyl)(phenyl)phosphine chloride;alternatively, (ethyl)(phenyl)phosphine chloride; alternatively,(isopropyl)(phenyl)phosphine chloride; alternatively,(tert-butyl)(phenyl)phosphine chloride; or alternatively,(neo-pentyl)(phenyl)phosphine chloride.

In some non-limiting embodiments, the phosphine halide can bedicyclopentylphosphine chloride, dicyclohexylphosphine chloride;alternatively, dicyclopentylphosphine chloride; or alternatively,dicyclohexylphosphine chloride.

In yet another non non-limiting aspect, the phosphine halide can bebis(2-fluorophenyl)-phosphine chloride, bis(2-chlorophenyl)phosphinechloride, bis(3-fluorophenyl)phosphine chloride,bis(3-chlorophenyl)phosphine chloride, bis(4-fluorophenyl)phosphinechloride, or bis(4-chlorophenyl)-phosphine chloride. In someembodiments, the phosphine halide can be bis(2-fluorophenyl)phosphinechloride, bis(3-fluorophenyl)phosphine chloride, orbis(4-fluorophenyl)phosphine chloride; or alternatively,bis(2-chlorophenyl)phosphine chloride, bis(3-chlorophenyl)phosphinechloride, or bis(4-chlorophenyl)phosphine chloride. In otherembodiments, the phosphine halide can be bis(2-fluoro-phenyl)phosphinechloride; alternatively, bis(2-chlorophenyl)phosphine chloride;alternatively, bis(3-fluorophenyl)phosphine chloride; alternatively,bis(3-chlorophenyl)phosphine chloride; alternatively,bis(4-fluorophenyl)phosphine chloride; or alternatively,bis(4-chlorophenyl)phosphine chloride.

In yet another non non-limiting aspect, the phosphine halide can be(2-fluorophenyl)(phenyl)-phosphine chloride,(2-chlorophenyl)(phenyl)phosphine chloride,(3-fluorophenyl)(phenyl)phosphine chloride,(3-chlorophenyl)(phenyl)phosphine chloride,(4-fluorophenyl)(phenyl)phosphine chloride, or(4-chlorophenyl)(phenyl)phosphine chloride. In some embodiments, thephosphine halide can be (2-fluorophenyl)(phenyl)phosphine chloride,(3-fluorophenyl)(phenyl)phosphine chloride, or(4-fluorophenyl)(phenyl)phosphine chloride; or alternatively,(2-chlorophenyl)(phenyl)phosphine chloride,(3-chlorophenyl)(phenyl)phosphine chloride, or(4-chlorophenyl)(phenyl)phosphine chloride. In other embodiments, thephosphine halide can be (2-fluorophenyl)(phenyl)phosphine chloride;alternatively, (2-chlorophenyl)(phenyl)phosphine chloride;alternatively, (3-fluorophenyl)(phenyl)-phosphine chloride;alternatively, (3-chlorophenyl)(phenyl)phosphine chloride;alternatively, (4-fluorophenyl)(phenyl)phosphine chloride; oralternatively, (4-chlorophenyl)(phenyl)phosphine chloride.

In yet another non non-limiting aspect, the phosphine halide can bediphenylphosphine chloride, bis(2-methylphenyl)phosphine chloride,bis(2-ethylphenyl)phosphine chloride, bis(2-isopropyl-phenyl)phosphinechloride, bis(2-tert-butylphenyl)phosphine chloride,bis(3-methylphenyl)phosphine chloride, bis(3-ethylphenyl)phosphinechloride, bis(3-isopropylphenyl)phosphine chloride,bis(3-tert-butylphenyl)phosphine chloride, diphenylphosphine chloride,bis(4-methylphenyl)phosphine chloride, bis(4-ethylphenyl)phosphinechloride, bis(4-isopropylphenyl)phosphine chloride, orbis(4-tert-butylphenyl)phosphine chloride. In an embodiment, thephosphine halide can be bis(2-methyl-phenyl)phosphine chloride,bis(2-ethylphenyl)phosphine chloride, bis(2-isopropylphenyl)phosphinechloride, or bis(2-tert-butylphenyl)phosphine chloride; alternatively,diphenylphosphine chloride, bis(3-methylphenyl)phosphine chloride,bis(3-ethylphenyl)phosphine chloride, bis(3-isopropylphenyl)-phosphinechloride, or bis(3-tert-butylphenyl)phosphine chloride; oralternatively, diphenylphosphine chloride, bis(4-methylphenyl)phosphinechloride, bis(4-ethylphenyl)phosphine chloride,bis(4-isopropyl-phenyl)phosphine chloride, orbis(4-tert-butylphenyl)phosphine chloride. In other embodiments, thephosphine halide can be diphenylphosphine chloride; alternatively,bis(2-methylphenyl)phosphine chloride; alternatively,bis(2-ethylphenyl)phosphine chloride; alternatively,bis(2-isopropylphenyl)-phosphine chloride; alternatively,bis(2-tert-butylphenyl)phosphine chloride; alternatively,bis(3-methyl-phenyl)phosphine chloride; alternatively,bis(3-ethylphenyl)phosphine chloride; alternatively,bis(3-isopropylphenyl)phosphine chloride; alternatively,bis(3-tert-butylphenyl)phosphine chloride; alternatively,diphenylphosphine chloride; alternatively, bis(4-methylphenyl)phosphinechloride; alternatively, bis(4-ethylphenyl)phosphine chloride,bis(4-isopropylphenyl)phosphine chloride; or alternatively,bis(4-tert-butylphenyl)phosphine chloride.

In yet another non non-limiting aspect, the phosphine halide can bediphenylphosphine chloride, (2-methylphenyl)(phenyl)phosphine chloride,(2-ethylphenyl)(phenyl)phosphine chloride,(2-isopropylphenyl)(phenyl)phosphine chloride,(2-tert-butylphenyl)(phenyl)phosphine chloride,(3-methylphenyl)(phenyl)phosphine chloride,(3-ethylphenyl)(phenyl)phosphine chloride,(3-isopropyl-phenyl)(phenyl)phosphine chloride,(3-tert-butylphenyl)(phenyl)phosphine chloride, diphenylphosphinechloride, (4-methylphenyl)(phenyl)phosphine chloride,(4-ethylphenyl)(phenyl)phosphine chloride,(4-isopropylphenyl)(phenyl)phosphine chloride, or(4-tert-butylphenyl)(phenyl)phosphine chloride. In an embodiment, thephosphine halide can be (2-methylphenyl)(phenyl)phosphine chloride,(2-ethylphenyl)-(phenyl)phosphine chloride,(2-isopropylphenyl)(phenyl)phosphine chloride, or(2-tert-butylphenyl)-(phenyl)phosphine chloride; alternatively,diphenylphosphine chloride, (3-methylphenyl)(phenyl)-phosphine chloride,(3-ethylphenyl)(phenyl)phosphine chloride,(3-isopropylphenyl)(phenyl)phosphine chloride, or(3-tert-butylphenyl)(phenyl)phosphine chloride; or alternatively,diphenylphosphine chloride, (4-methylphenyl)(phenyl)phosphine chloride,(4-ethylphenyl)(phenyl)phosphine chloride,(4-isopropyl-phenyl)(phenyl)phosphine chloride, or(4-tert-butylphenyl)(phenyl)phosphine chloride. In other embodiments,the phosphine halide can be diphenylphosphine chloride; alternatively,(2-methylphenyl)-(phenyl)phosphine chloride; alternatively,(2-ethylphenyl)(phenyl)phosphine chloride; alternatively,(2-isopropylphenyl)(phenyl)phosphine chloride; alternatively,(2-tert-butylphenyl)(phenyl)phosphine chloride; alternatively,(3-methylphenyl)(phenyl)phosphine chloride; alternatively,(3-ethylphenyl)-(phenyl)phosphine chloride; alternatively,(3-isopropylphenyl)(phenyl)phosphine chloride; alternatively,(3-tert-butylphenyl)(phenyl)phosphine chloride; alternatively,diphenylphosphine chloride; alternatively,(4-methylphenyl)(phenyl)phosphine chloride; alternatively,(4-ethylphenyl)(phenyl)phosphine chloride,(4-isopropylphenyl)(phenyl)phosphine chloride; or alternatively,(4-tert-butylphenyl)(phenyl)phosphine chloride.

In yet another non-limiting aspect, the phosphine halide can bediphenylphosphine chloride, bis(2-methoxyphenyl)phosphine chloride,bis(2-ethoxyphenyl)phosphine chloride, bis(2-isopropoxy-phenyl)phosphinechloride, bis(2-tert-butoxyphenyl)phosphine chloride,bis(3-methoxyphenyl)phosphine chloride, bis(3-ethoxyphenyl)phosphinechloride, bis(3-isopropoxyphenyl)phosphine chloride,bis(3-tert-butoxyphenyl)phosphine chloride, diphenoxyphosphine chloride,bis(4-methoxyphenyl)-phosphine chloride, bis(4-ethoxyphenyl)phosphinechloride, bis(4-isopropoxyphenyl)phosphine chloride, orbis(4-tert-butoxyphenyl)phosphine chloride. In an embodiment, thephosphine halide can be bis(2-methoxyphenyl)phosphine chloride,bis(2-ethoxyphenyl)phosphine chloride, bis(2-isopropoxy-phenyl)phosphinechloride, or bis(2-tert-butoxyphenyl)phosphine chloride; alternatively,diphenoxyphosphine chloride, bis(3-methoxyphenyl)phosphine chloride,bis(3-ethoxyphenyl)phosphine chloride, bis(3-isopropoxyphenyl)phosphinechloride, or bis(3-tert-butoxyphenyl)phosphine chloride; oralternatively, diphenoxyphosphine chloride,bis(4-methoxyphenyl)phosphine chloride, bis(4-ethoxy-phenyl)phosphinechloride, bis(4-isopropoxyphenyl)phosphine chloride, orbis(4-tert-butoxyphenyl)-phosphine chloride. In other embodiments, thephosphine halide can be diphenylphosphine chloride; alternatively,bis(2-methoxyphenyl)phosphine chloride; alternatively,bis(2-ethoxyphenyl)phosphine chloride; alternatively,bis(2-isopropoxyphenyl)phosphine chloride; alternatively,bis(2-tert-butoxy-phenyl)phosphine chloride; alternatively,bis(3-methoxyphenyl)phosphine chloride; alternatively,bis(3-ethoxyphenyl)phosphine chloride; alternatively,bis(3-isopropoxyphenyl)phosphine chloride; alternatively,bis(3-tert-butoxyphenyl)phosphine chloride; alternatively,diphenoxyphosphine chloride; alternatively,bis(4-methoxyphenyl)phosphine chloride; alternatively,bis(4-ethoxyphenyl)phosphine chloride, bis(4-isopropoxyphenyl)phosphinechloride; or alternatively, bis(4-tert-butoxyphenyl)phosphine chloride.

In yet another non non-limiting aspect, the phosphine halide can bediphenylphosphine chloride, (2-methoxyphenyl)(phenyl)phosphine chloride,(2-ethoxyphenyl)(phenyl)phosphine chloride,(2-isopropoxyphenyl)(phenyl)phosphine chloride,(2-tert-butoxyphenyl)(phenyl)phosphine chloride,(3-methoxyphenyl)(phenyl)phosphine chloride,(3-ethoxyphenyl)(phenyl)phosphine chloride,(3-isopropoxyphenyl)(phenyl)phosphine chloride,(3-tert-butoxyphenyl)(phenyl)phosphine chloride, diphenoxyphosphinechloride, (4-methoxyphenyl)(phenyl)phosphine chloride,(4-ethoxyphenyl)(phenyl)-phosphine chloride,(4-isopropoxyphenyl)(phenyl)phosphine chloride, or(4-tert-butoxyphenyl)(phenyl)-phosphine chloride. In an embodiment, thephosphine halide can be (2-methoxyphenyl)(phenyl)-phosphine chloride,(2-ethoxyphenyl)(phenyl)phosphine chloride,(2-isopropoxyphenyl)(phenyl)-phosphine chloride, or(2-tert-butoxyphenyl)(phenyl)phosphine chloride; alternatively,diphenoxyphosphine chloride, (3-methoxyphenyl)(phenyl)phosphinechloride, (3-ethoxyphenyl)(phenyl)phosphine chloride,(3-isopropoxyphenyl)(phenyl)phosphine chloride, or(3-tert-butoxyphenyl)(phenyl)phosphine chloride; or alternatively,diphenoxyphosphine chloride, (4-methoxyphenyl)(phenyl)phosphinechloride, (4-ethoxyphenyl)(phenyl)phosphine chloride,(4-isopropoxyphenyl)(phenyl)phosphine chloride, or(4-tert-butoxyphenyl)(phenyl)phosphine chloride. In other embodiments,the phosphine halide can be diphenylphosphine chloride; alternatively,(2-methoxyphenyl)(phenyl)phosphine chloride; alternatively,(2-ethoxyphenyl)(phenyl)phosphine chloride; alternatively,(2-isopropoxyphenyl)(phenyl)phosphine chloride; alternatively,(2-tert-butoxyphenyl)(phenyl)phosphine chloride; alternatively,(3-methoxy-phenyl)(phenyl)phosphine chloride; alternatively,(3-ethoxyphenyl)(phenyl)phosphine chloride; alternatively,(3-isopropoxyphenyl)(phenyl)phosphine chloride; alternatively,(3-tert-butoxyphenyl)-(phenyl)phosphine chloride; alternatively,diphenoxyphosphine chloride; alternatively,(4-methoxy-phenyl)(phenyl)phosphine chloride; alternatively,(4-ethoxyphenyl)(phenyl)phosphine chloride,(4-isopropoxyphenyl)(phenyl)phosphine chloride; or alternatively,(4-tert-butoxyphenyl)(phenyl)-phosphine chloride.

Generally, the phosphine halide and the metal formamidinate can becombined at a phosphine halide to metal formamidinate equivalent ratioof at least 0.9:1. In some embodiments, the phosphine halide and themetal formamidinate can be combined at a phosphine halide to metalformamidinate equivalent ratio of at least 0.95:1; alternatively, of atleast 0.975:1; or alternatively, of at least 0.99:1. In someembodiments, the phosphine halide and the metal formamidinate can becombined at a phosphine halide to metal formamidinate equivalent ratioranging from 0.9:1 to 1.25:1; alternatively, ranging from 0.95:1 to1.20:1; alternatively, ranging from 0.975:1 to 1.15:1; or alternatively,ranging from 0.99:1 to 1.10:1. In other embodiments, the phosphinehalide and the metal formamidinate can be combined at a phosphine halideto metal formamidinate equivalent ratio of about 1:1.

In an embodiment, the conditions capable of forming an N²-phosphinylformamidine compound can include a reaction temperature of at least 0°C.; alternatively, of at least 5° C.; alternatively, of at least 10° C.;or alternatively, of at least 15° C. In some embodiments, the conditionscapable of forming an N²-phosphinyl formamidine compound can include areaction temperature ranging from 0° C. to 60° C.; alternatively,ranging from 5° C. to 50° C.; alternatively, ranging from 10° C. to 45°C.; or alternatively, ranging from 15° C. to 40° C. In an embodiment,the conditions capable of forming an N²-phosphinyl formamidine compoundcan include a reaction time of at least 5 minutes; alternatively, of atleast 10 minutes; alternatively, of at least 15 minutes; oralternatively, of at least 20 minutes. In some embodiments, theconditions capable of forming an N²-phosphinyl formamidine compound caninclude a reaction time ranging from 5 minutes to 6 hours;alternatively, ranging from 10 minutes to 5 hours; alternatively,ranging from 15 minutes to 4.5 hours; or alternatively, ranging from 20minutes to 4 hours.

In an embodiment, the phosphine halide and the metal formamidinate canbe contacted in an aprotic solvent. In some embodiments, the phosphinehalide and the metal formamidinate can be contacted in a polar aproticsolvent. Aprotic solvents which can be utilized include hydrocarbonsolvents and ether solvents. Polar aprotic solvents which can beutilized include ether solvents. Solvents are generally disclosed hereinand any general or specific aprotic solvent and/or polar aprotic solventdescribed herein can be utilized to further describe the method ofpreparing an N²-phosphinyl formamidine compound comprising contacting aphosphine halide with a metal amidinate and forming the N²-phosphinylamidinate.

In an embodiment, the N²-phosphinyl formamidine compound can be utilizedwithout further isolation or purification. In some embodiments, theN²-phosphinyl formamidine compound can be isolated; or alternativelyisolated and purified. In an embodiment, wherein the N²-phosphinylformamidine compound can be prepared in a solvent (aprotic or polaraprotic), the method to prepare the N²-phosphinyl formamidine compoundcan include a step of isolating the N²-phosphinyl formamidine compoundby evaporating the solvent. In an embodiment wherein the N²-phosphinylformamidine compound can prepared in a solvent (aprotic or polaraprotic), the method to prepare the N²-phosphinyl formamidine compoundcan include the step of isolating the N²-phosphinyl formamidine compoundby filtering the solution to remove particulate materials and/orbyproducts of the reaction and evaporating the solvent. In embodiments,the method to prepare the N²-phosphinyl formamidine compound can includea purification step wherein the N²-phosphinyl formamidine compound canbe purified by dissolving the N²-phosphinyl formamidine compound in asolvent and filtering the solution to remove particulate materialsand/or byproducts of the reaction. The solvent utilized to purify theN²-phosphinyl formamidine compound can be the same solvent utilized toform the N²-phosphinyl formamidine compound or it can be different thanthe solvent utilized to form the N²-phosphinyl formamidine compound. Insome embodiments, the method to prepare the N²-phosphinyl formamidinecompound can include a purification step of washing the N²-phosphinylformamidine compound with a solvent. In other embodiments, the method toprepare the N²-phosphinyl formamidine compound can include apurification step of recrystallizing the N²-phosphinyl formamidinecompound.

Generally, evaporation of the solvent can be performed using anysuitable method. In some embodiments, the solvent can be evaporated atambient temperature (15-35° C.—no applied external heat source). Inother embodiments, the solvent can be evaporated with gentle heating(e.g., at a temperature ranging from 25° C. to 50° C.). In furtherembodiments, the solvent can be evaporated at ambient temperature underreduced pressure. In yet other embodiments, the solvent can beevaporated with gentle heating under reduced pressure.

Method of Preparing Metal Formamidinates

In an aspect, the metal formamidinate utilized in the method to preparethe N²-phosphinyl formamidine can be prepared by a) contacting anformamidine compound having an N² hydrogen atom with a metallic compoundcapable of abstracting a proton from a —NH₂ group or a >NH group; and b)forming the metal formamidinate. Generally, the metal formamidinate canbe formed under conditions capable of forming a metal formamidinate. Insome embodiments, the metal formamidinate can be isolated;alternatively, purified; or alternatively, isolated and purified.

In an embodiment, the formamidine compound can have Structure FA1 orFA2; alternatively, Structure FA1; or alternatively, Structure FA2. Insome embodiments, the formamidine compounds can have only one N²hydrogen atom (i.e., R³ is a non-hydrogen group in the formamidinecompound FA1). In other embodiments, the formamidine can have two N²hydrogen atoms (i.e., R³ is a hydrogen group in the formamidine compoundFA2).

Generally, the formamidine structure prefaced with FA corresponds to themetal formamidinate structure prefaced with MFA having the same numberdesignation. However, it should be noted that methods described hereinprovide for the conversion of formamidine compounds having Structure FA2(wherein R³ is hydrogen) into formamidine compounds having Structure FA1(wherein R³ is not hydrogen), respectively. R¹ and R³ within formamidinecompound Structures FA1 and/or FA2 are independently described asfeatures of the N²-phosphinyl formamidine compound Structures NPF1and/or NPF2. Since formamidine FA1 and/or FA2 can be utilized to prepareembodiments of N²-phosphinyl formamidine compounds having StructuresNPF1 and/or NPF2, the R¹ and R³ descriptions for the N²-phosphinylformamidine compounds can be utilized without limitation to furtherdescribe the formamidine Structures FA1 and/or FA2.

In an embodiment, the metallic compound capable of abstracting a protonfrom a —NH₂ group or a >NH group can be a metal hydride or a metalalkyl; alternatively, a metal hydride; or alternatively, a metal alkyl.In an embodiment the metal hydride can be sodium hydride, calciumhydride, lithium aluminum hydride or sodium borohydride; alternatively,sodium hydride or calcium hydride; alternatively, lithium aluminumhydride or sodium borohydride; alternatively, sodium hydride;alternatively, calcium hydride; alternatively, lithium aluminum hydride;or alternatively, sodium borohydride. Metal alkyl compounds aredescribed herein and can be utilized, without limitation, as the metalalkyl for abstracting the proton from the formamidine compound. Usefulmetal alkyls for abstracting the proton from the formamidine compoundcan be Group 1 metal alkyls or Group 2 metal alkyls; alternatively,Group 1 metal alkyls; or alternatively, Group 2 metal alkyls. In anembodiment, the metal alkyl can be a lithium alkyl, a sodium alkyl, or apotassium alkyl; alternatively, a lithium alkyl or a sodium alkyl;alternatively, a lithium alkyl; alternatively, a sodium alkyl; oralternatively, a potassium alkyl. Alkyl groups for the metal alkyl aredescribed herein and can be utilized without limitation to furtherdescribe the metal alkyls which can be contacted with the formamidinecompound. In some exemplary embodiments, the metal alkyl can be methyllithium, n-butyl lithium, sec-butyl lithium, or tert-butyl lithium;alternatively, methyl lithium; alternatively, n-butyl lithium;alternatively, sec-butyl lithium; or alternatively, tert-butyl lithium.

Generally, the formamidine compound and the metallic compound capable ofabstracting a proton from a —NH₂ group or a >NH group can be combined ina formamidine compound to metallic compound equivalent ratio of at least0.9:1. In an embodiment, the formamidine compound and the metalliccompound capable of abstracting a proton from a —NH₂ group or a >NHgroup can be combined in a formamidine compound to metallic compoundequivalent ratio of at least 0.95:1; alternatively, of at least 0.975:1;or alternatively, of at least 0.99:1. In some embodiments, theformamidine compound and the metallic compound capable of abstracting aproton from a —NH₂ group or a >NH group can be combined in a formamidinecompound and metallic compound equivalent ratio ranging from 0.9:1 to1.25:1; alternatively, ranging from 0.95:1 to 1.20:1; alternatively,ranging from 0.975:1 to 1.15:1; or alternatively, ranging from 0.99:1 to1.10:1. In other embodiments, the formamidine compound and the metalliccompound capable of abstracting a proton from a —NH₂ group or a >NHgroup can be combined in a formamidine compound to metallic compoundequivalent ratio of about 1:1.

In an embodiment, the conditions capable of forming the metalformamidinate can include a temperature of at least −45° C.;alternatively, of at least −30° C.; alternatively, of at least −25° C.;or alternatively, of at least −20° C. In some embodiments, the reactionconditions capable of forming a metal formamidinate can include atemperature ranging from −45° C. to 60° C.; alternatively, ranging from−30° C. to 50° C.; alternatively, ranging from −25° C. to 45° C.; oralternatively, ranging from −20° C. to 40° C.

In some embodiments, the conditions capable of forming the metalformamidinate can include an initial metallic compound capable ofabstracting a proton from a —NH₂ group or a >NH group and formamidinecompound, contact temperature, and a second temperature to form themetal formamidinate. It should be noted the when the conditions capableof forming the metal formamidinate is described as occurring at twotemperatures (one for the contact of the metallic compound capable ofabstracting a proton from a —NH₂ group or a >NH group and theformamidine compound and one for the formation of the metalformamidinate) that this description does not exclude the prospect thatmetal formamidinate can be formed at the contact temperature. Thedescription just relates that, in some embodiments, the metalformamidinate formation can proceed better when the initial contactbetween the metallic compound capable of abstracting a proton from a—NH₂ group or a >NH group and formamidine compound is performed at onetemperature and the formation of the metal formamidinate is completed ata second different temperature.

In an embodiment, the metallic compound capable of abstracting theproton from a formamidine compound and formamidine compound can becontacted at a temperature ranging from −45° C. to 20° C.;alternatively, ranging from −30° C. to 15° C.; alternatively, rangingfrom −25° C. to 45° C.; or alternatively, ranging from −20° C. to 40° C.In an embodiment, the metal formamidinate can be formed at a temperatureranging from 0° C. to 20° C.; alternatively, ranging from 5° C. to 15°C.; alternatively, ranging from 10° C. to 45° C.; or alternatively,ranging from 15° C. to 40° C.

In an embodiment, the conditions capable of forming the metalformamidinate can include a metal formamidinate formation time of atleast 5 minutes; alternatively, of at least 10 minutes; alternatively,of at least 15 minutes; or alternatively, of at least 20 minutes. Insome embodiments, the conditions capable of forming the metalformamidinate can include a metal formamidinate formation time rangingfrom 5 minutes to 6 hours; alternatively, ranging from 10 minutes to 5hours; alternatively, ranging from 15 minutes to 4.5 hours; oralternatively, ranging from 20 minutes to 4 hours.

In an embodiment, the metallic compound capable of abstracting a protonfrom a —NH₂ group or a >NH group and the formamidine compound can becontacted in an aprotic solvent. In some embodiments, the metalliccompound capable of abstracting a proton from a —NH₂ group or a >NHgroup and the formamidine compound can be contacted in a polar aproticsolvent. Aprotic solvents which can be utilized include hydrocarbonsolvents and ether solvents. Polar aprotic solvents which can beutilized include ether solvents. Solvents are generally disclosed hereinand any general or specific aprotic solvent and/or polar aprotic solventdescribed herein can be utilized to further describe the method ofpreparing the metal formamidinate by contacting a metallic compoundcapable of abstracting a proton from a —NH₂ group or a >NH group and anformamidine compound and forming a metal amidinate.

In an embodiment, the metal formamidinate can be utilized withoutfurther isolation or purification. In some embodiments, the metalformamidinate can be isolated; alternatively, purified; oralternatively, isolated and purified. In an embodiment, the method toprepare the metal formamidinate can include a step of isolating themetal formamidinate by filtering the metal formamidate from thesolution. In some embodiments, the method to prepare the metalformamidinate can include a step of purifying the metal formamidinate bywashing the metal formamidinate with a solvent. Generally, the washingsolvent can be an aprotic solvent. In other embodiments, the washingsolvent can be a polar aprotic solvent. In other embodiments, thewashing solvent can be a non-polar aprotic solvent.

Formamidine Compounds and Hydrocarboxymethanimine Compounds

In an aspect, the formamidine compounds which can be utilized to formthe N²-phosphinyl formamidine compound can be prepared by a methodcomprising contacting an amine and a trihydrocarbylformate to form aformamidine compound; or alternatively, 1) contacting an amine and atrihydrocarbylformate to form a hydrocarboxymethanimine compound and 2)contacting the hydrocarboxymethanimine compound and an ammonium compoundto form a formamidine compound. In some embodiments, the formamidinecompound which can be utilized to form the N²-phosphinyl formamidinecompound can be prepared by a method comprising: a) contacting an amineand a trihydrocarbylformate; and b) forming the formamidine compound;alternatively, a) contacting an amine and a trihydrocarbylformate, b)forming a hydrocarboxymethanimine compound, c) contacting thehydrocarboxymethanimine compound and an ammonium compound, and d)forming the formamidine compound. In an embodiment, the amine and thetrihydrocarbylformate are contacted in the presence of acid catalyst. Insuch embodiments, a formamidine compound can be prepared by a methodcomprising contacting an amine, a trihydrocarbylformate, and an acidcatalyst to form the formamidine compound; or alternatively, ahydrocarboxymethanime compound can be prepared by the method comprisingcontacting an amine, a trihydrocarbylformate, and an acid catalyst toform the hydrocarboxymethanime compound. The formamidine compound can beformed under conditions capable of forming a formamidine. In someembodiments, the formamidine compound can be isolated; alternatively,purified; or alternatively, isolated and purified. Thehydrocarboxymethanimine compound can be formed under conditions capableof forming a hydrocarboxymethanimine. In some embodiments, thehydrocarboxymethanimine compound can be isolated; alternatively,purified; or alternatively, isolated and purified. General and specificamines and trihydrocarbylformates are disclosed herein and these generaland specific amines and trihydrocarbylformates can be utilized, withoutlimitation, to further describe the method to prepare the formamidinecompound.

In an embodiment, the amine can have Structure A1. R¹ within amineStructure A1 isR¹—NH₂  Structure A1independently described as a feature of the N²-phosphinyl formamidinecompound having Structure NPF1 and/or NPF2. Since amines havingStructure A1 are ultimately utilized to prepare embodiments ofN²-phosphinyl formamidine compounds having Structures NPF1 and/or NPF2,the R¹ descriptions for the N²-phosphinyl formamidine compounds can beutilized without limitation to further describe the amine Structure A1.

In an aspect, the amine having Structure A1 can be methylamine, anethylamine, a propylamine, a butylamine, a pentylamine, a hexylamine, aheptylamine, an octylamine, a nonylamine, or a decylamine. In someembodiments, the amine having Structure A1 can be methylamine,ethylamine, n-propylamine, iso-propylamine, n-butylamine,iso-butylamine, sec-butylamine, tert-butylamine, n-pentylamine,iso-pentylamine, sec-pentylamine, or neopentylamine; alternatively,methylamine, ethylamine, iso-propylamine, tert-butylamine, orneopentylamine; alternatively, methylamine; alternatively, ethylamine;alternatively, n-propylamine; alternatively, iso-propylamine;alternatively, tert-butylamine; or alternatively, neopentylamine. Inother aspects, the amine having Structure A1 can be cyclobutylamine, asubstituted cyclobutylamine, cyclopentylamine, a substitutedcyclopentylamine, cyclohexylamine, a substituted cyclohexylamine,cycloheptylamine, a substituted cycloheptylamine, cyclooctylamine, or asubstituted cyclooctylamine. In an embodiment the amine having StructureA1 can be cyclopentylamine, a substituted cyclopentylamine,cyclohexylamine, or a substituted cyclohexylamine. In other embodiments,the amine having Structure A1 can be cyclobutylamine or a substitutedcyclobutylamine; alternatively, a cyclopentylamine or a substitutedcyclopentylamine; alternatively, a cyclohexylamine or a substitutedcyclohexylamine; alternatively, a cycloheptylamine or a substitutedcycloheptylamine; or alternatively, a cyclooctylamine, or a substitutedcyclooctylamine. In further embodiments, the amine having Structure A1can be cyclopentylamine; alternatively, a substituted cyclopentylamine;a cyclohexylamine; or alternatively, a substituted cyclohexylamine.Substituents and substituents patterns for the R¹ cycloalkyl groups aredescribed herein and can be utilized without limitation to furtherdescribe the substituted cycloalkylamines which can be utilized as theamine having Structure A1 in aspects and/or embodiments describedherein.

In an aspect, the amine having Structure A1 can have Structure A6 or A7

The R^(11c), R^(31c), R^(12c), R^(32c), R^(13c), R^(33c), R^(14c),R^(34c), R^(15c) and R^(35c) substituents, substituent patterns, and nfor the R¹ group in Structure G1 are described herein and can beutilized without limitation to describe the amine having Structure A6and/or Structure A7 which can be utilized in the various aspects andembodiments described herein.

In an aspect, the amine having Structure A1 can be aniline, asubstituted aniline, a naphthylamine, or a substituted naphthylamine. Inan embodiment, R¹ can be aniline or a substituted aniline;alternatively, a naphthylamine or a substituted naphthylamine;alternatively, an aniline or a naphthylamine; or alternatively, asubstituted aniline or a substituted naphthylamine. Substituents andsubstituents patterns for R¹ are described herein and can be utilizedwithout limitation to further describe the substituted anilines andsubstituted naphthylamines which can be utilized in aspects and/orembodiments described herein.

In an embodiment, the amine having Structure A1 can be a 2-substitutedaniline, a 3-substituted aniline, a 4-substituted aniline, a2,4-disubstituted aniline, a 2,6-disubstituted aniline,3,5-disubstituted aniline, or a 2,4,6-trisubstituted aniline. In otherembodiments, the R¹ substituted aniline can be a 2-substituted aniline,a 4-substituted aniline, a 2,4-disubstituted aniline, or a2,6-disubstituted aniline; alternatively, a 3-substituted aniline or a3,5-disubstituted aniline; alternatively, a 2-substituted aniline or a4-substituted aniline; alternatively, a 2,4-disubstituted aniline or a2,6-disubstituted aniline; alternatively, a 2-substituted aniline;alternatively, a 3-substituted aniline; alternatively, a 4-substitutedaniline; alternatively, a 2,4-disubstituted aniline; alternatively, a2,6-disubstituted aniline; alternatively, 3,5-disubstituted aniline; oralternatively, a 2,4,6-trisubstituted aniline. Substituents for the R¹phenyl groups are generally disclosed herein and can be utilized withoutlimitation to further describe the substituted anilines which can beutilized in the various aspects and/or embodiments described herein.

In an embodiment, the amine having Structure A1 can be 1-naphthylamine,a substituted 1-naphthylamine, 2-naphthylamine, or a substituted2-naphthylamine. In some embodiments, the amine having Structure A1 canbe 1-naphthylamine or a substituted 1-naphthylamine; alternatively,2-naphthylamine or a substituted 2-naphthylamine; alternatively,1-naphthylamine; alternatively, a substituted 1-naphthylamine;alternatively, 2-naphthylamine; or alternatively, a substituted2-naphthylamine. In other embodiments, the amine having Structure A1 canbe a 2-substituted 1-naphthylamine, a 3-substituted 1-naphthylamine, a4-substituted 1-naphthylamine, or a 8-substituted 1-naphthylamine;alternatively, a 2-substituted 1-naphthylamine; alternatively, a3-substituted 1-naphthylamine; alternatively, a 4-substituted1-naphthylamine; or alternatively, a 8-substituted 1-naphthylamine. Infurther embodiments, the amine having Structure A1 can be a1-substituted 2-naphthylamine, a 3-substituted 2-naphthylamine, or a4-substituted 2-naphthylamine, or a 1,3-disubstituted 2-naphthylamine;alternatively, a 1-substituted 2-naphthylamine; alternatively, a3-substituted 2-naphthylamine; alternatively, a 4-substituted2-naphthylamine; alternatively, or a 1,3-disubstituted 2-naphthylamine.Substituents for the R¹ naphthyl groups are generally disclosed hereinand can be utilized without limitation to further describe thesubstituted naphthylamines which can be utilized in the various aspectsand/or embodiments described herein.

In an aspect, the amine having Structure A1 can have Structure A8.

The R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ substituents and substituent patternsfor the R¹ group having Structure G2 are described herein and can beutilized without limitation to describe the amine having Structure A8which can be utilized in the various aspects and embodiments describedherein.

In a non-limiting embodiment, the amine having Structure A1 can beaniline, a 2-alkylaniline, a 3-alkylaniline, a 4-alkylaniline, a2,4-dialkylaniline a 2,6-dialkylaniline, a 3,5-dialkylaniline, or a2,4,6-trialkylaniline; alternatively, a 2-alkylaniline, a4-alkylaniline, a 2,4-dialkylaniline, a 2,6-dialkylaniline, or a2,4,6-trialkylaniline; alternatively, a 2-alkylaniline or a4-alkylaniline; alternatively, a 2,4-dialkylaniline a2,6-dialkylaniline; alternatively, a 3-alkylaniline or a3,5-dialkylaniline; alternatively, a 2-alkylaniline or a2,6-dialkylaniline; alternatively, a 2-alkylaniline; alternatively, a3-alkylaniline; alternatively, a 4-alkylaniline; alternatively, a2,4-dialkylaniline; alternatively, a 2,6-dialkylaniline; alternatively,a 3,5-dialkylaniline; or alternatively, a 2,4,6-trialkylaniline. Inanother non-limiting embodiment, the amine having Structure A1 can be a1-aminonaphthylene, a 2-aminonaphthylene, a 2-alkylnaphth-1-yl group, a1-alkyl-2-aminonaphthylene, a 3-alkylnapth-2-yl group, or a1,3-dialkyl-2-aminonaphthylene; alternatively, a 1-aminonaphthylene or a2-alkyl-1-amino-naphthylene; alternatively, a 2-aminonaphthylene, a1-alkyl-2-aminonaphthylene, a 3-alkylamin-napthylene, or a1,3-dialkyl-2-aminonaphthylene; alternatively, 1-aminonaphthylene;alternatively, a 2-aminonaphthylene; alternatively, a2-alkyl-1-aminonaphthylene; alternatively, a 1-alkyl-2-aminonaphthylene;alternatively, a 3-alkyl-2-aminonapthylene; or alternatively, a1,3-dialkyl-2-aminonaphthylene. In other non-limiting embodiments, theamine having Structure A1 can be a cyclohexylamine, a2-alkylcyclohexylamine, or a 2,6-dialkylcyclohexylamine; alternatively,cyclopentylamine, a 2-alkylcyclopentylamine, or a2,5-dialkylcyclopentylamine; alternatively, cyclohexylamine;alternatively, a 2-alkylcyclohexylamine; alternatively, a2,6-dialkylcyclohexylamine; alternatively, cyclopentylamine;alternatively, a 2-alkylcyclopentylamine; or alternatively,2,5-dialkylcyclopentylamine. Alkyl group substituents are independentlydescribed herein and can be utilized, without limitation, to furtherdescribe the alkylanilines, dialkylanilines, trialkylanilines,alkylaminonaphthylenes, dialkylaminonaphthylenes, alkylcyclohexylamines,dialkylcyclohexylamines, alkylcyclopentylamines, ordialkylcyclopentylamine which can be utilized in the various aspectsand/or embodiments described herein. Generally, the alkyl substituentsof a dialkyl or trialkyl anilines, aminonaphthylenes, cyclohexylamines,or cyclopentylamines can be the same; or alternatively, can bedifferent.

In another non-limiting embodiment, the amine having Structure A1 can beaniline, a 2-alkoxyaniline, a 3-alkoxyaniline, a 4-alkoxyaniline, or a3,5-dialkoxyaniline; alternatively, a 2-alkoxyaniline or a4-alkoxyaniline; alternatively, a 3-alkoxyaniline or3,5-dialkoxyaniline; alternatively, a 2-alkoxyaniline, alternatively, a3-alkoxyaniline; alternatively, a 4-alkoxyaniline; alternatively, a3,5-dialkoxyaniline. Alkoxy group substituents are independentlydescribed herein and can be utilized, without limitation, to furtherdescribe the alkoxyanilines or dialkoxyanilines which can be utilized inthe various aspects and/or embodiments described herein. Generally, thealkoxy substituents of a dialkoxyaniline can be the same; oralternatively, can be different.

In other non-limiting embodiments, the amine having Structure A1 can beaniline, a 2-haloaniline, a 3-haloaniline, a 4-haloaniline, a2,6-dihalophenylgroup, or a 3,5-dialkylaniline; alternatively, a2-haloaniline, a 4-haloaniline, or a 2,6-dihaloaniline; alternatively, a2-haloaniline or a 4-haloaniline; alternatively, a 3-haloaniline or a3,5-dihaloaniline; alternatively, a 2-haloaniline; alternatively, a3-haloaniline; alternatively, a 4-haloaniline; alternatively, a2,6-dihaloaniline; or alternatively, a 3,5-dialkylaniline. Halides areindependently described herein and can be utilized, without limitation,to further describe the haloanilines or dihaloanilines which can beutilized in the various aspects and/or embodiments described herein.Generally, the halides of a dihaloaniline can be the same; oralternatively, can be different.

In a non-limiting embodiment, the amine having Structure A1 can be2-methylaniline, 2-ethylaniline, 2-n-propylaniline, 2-isopropylaniline,2-tert-butylaniline, 3-methylaniline, 2,6-dimethylaniline,2,6-diethylaniline, 2,6-di-n-propylaniline, 2,6-diisopropylaniline,2,6-di-tert-butylaniline, 2-isopropyl-6-methylaniline, or2,4,6-trimethylaniline; alternatively, 2-methylaniline, 2-ethylaniline,2-n-propylaniline, 2-isopropylaniline, or 2-tert-butylaniline;alternatively, 2,6-dimethylaniline, 2,6-diethylaniline,2,6-di-n-propylaniline, 2,6-diisopropylaniline,2,6-di-tert-butylaniline, or 2-isopropyl-6-methylaniline; alternatively,2-methylaniline; alternatively, 2-ethylaniline; alternatively,2-n-propylaniline; alternatively, 2-isopropylaniline; alternatively,2-tert-butylaniline; alternatively, 3-methylaniline; alternatively,2,6-dimethylaniline; alternatively, 2,6-diethylaniline; alternatively,2,6-di-n-propylaniline; alternatively, 2,6-diisopropylaniline;alternatively, 2,6-di-tert-butylaniline; alternatively,2-isopropyl-6-methylaniline; alternatively, 3,5-dimethylaniline; oralternatively, 2,4,6-trimethylaniline. In another non-limitingembodiment, the amine having Structure A1 can be2-methylcyclohexylamine, 2-ethylcyclohexylamine,2-isopropylcyclohexylamine, 2-tert-butylcyclohexylamine,2,6-dimethylcyclohexylamine, 2,6-diethylcyclohexylamine,2,6-diisopropylcyclohexylamine, or 2,6-di-tert-butylcyclohexylamine;alternatively, 2-methylcyclohexylamine, 2-ethylcyclohexylamine,2-isopropylcyclohexylamine, or 2-tert-butylcyclohexylamine;alternatively, 2,6-dimethylcyclohexylamine, 2,6-diethylcyclohexylamine,2,6-diisopropylcyclohexylamine, or 2,6-di-tert-butylcyclohexylamine;alternatively, 2-methylcyclohexyl; alternatively,2-ethylcyclohexylamine; alternatively, 2-isopropylcyclohexylamine;alternatively, 2-tert-butylcyclohexylamine; alternatively,2,6-dimethylcyclohexylamine; alternatively, 2,6-diethylcyclohexylamine;alternatively, 2,6-diisopropylcyclohexylamine; or alternatively, or2,6-di-tert-butylcyclohexylamine. In another non-limiting embodiment,the amine having Structure A1 can be 2-methyl-1-aminonaphthylene,2-ethyl-1-aminonaphthylene group, 2-n-propyl-1-aminonaphthylene,2-isopropyl-1-aminoenaphthylene group, or2-tert-butyl-1-aminonaphthylene group; alternatively,2-methyl-1-aminonaphthylene group; alternatively,2-ethyl-1-aminonaphthylene group; alternatively,2-n-propyl-1-aminonaphthylene group; alternatively,2-isopropyl-1-naphthylene group; or alternatively,2-tert-butyl-1-amononaphthylene group.

In a non-limiting embodiment, the amine having Structure A1 can be3-methoxyaniline, 3-ethoxyaniline, 3-isoprooxyaniline,3-tert-butoxyaniline, 4-methoxyaniline, 4-ethoxyaniline,4-isopropoxyaniline, 4-tert-butoxyaniline, 3,5-dimethoxyaniline,3,5-diethoxyaniline, 3,5-diisopropoxyaniline, or3,5-di-tert-butoxyaniline; alternatively, 3-methoxyaniline,3-ethoxyaniline, 3-isopropoxyaniline, or 3-tert-butoxyaniline;alternatively, 4-methoxyaniline, 4-ethoxyaniline, 4-isopropoxyaniline,or 4-tert-butoxyaniline; or alternatively, 3,5-dimethoxyaniline,3,5-diethoxyaniline, 3,5-diisopropoxyaniline, or3,5-di-tert-butoxyaniline. In other non-limiting embodiments, the aminehaving Structure A1 can be 3-methoxyaniline; alternatively,3-ethoxyaniline; alternatively, 3-isopropoxyaniline; alternatively,3-tert-butoxyaniline; alternatively, 4-methoxyaniline; alternatively,4-ethoxyaniline; alternatively, 4-isopropoxyaniline; alternatively,4-tert-butoxyaniline; alternatively, 3,5-dimethoxyaniline;alternatively, 3,5-diethoxyaniline; alternatively,3,5-diisopropoxyaniline; or alternatively, 3,5-di-tert-butoxyaniline.

In an embodiment, when a nitrogen atom of the amine group is attached toa ring atom (e.g. aminocycloalkane, aromatic amine, or aminoarene), theamine can comprise at least one substituent located on a carbon atomadjacent to the ring carbon atom attached to the nitrogen atom of theamine group; or alternatively, the amine can comprise at least onesubstituent at each carbon atom adjacent to the ring carbon atomattached to the nitrogen atom of the amine group. In some embodiments,when the nitrogen atom of the amine group is attached to a ring atom(e.g. aminocycloalkane, aromatic amine, or aminoarene,), the amine canconsist of one substituent located on a carbon atom adjacent to the ringcarbon atom attached to the nitrogen atom of the amine group. In someembodiments, when the nitrogen atom of the amine group is attached to aring atom (e.g. aminocycloalkane, aromatic amine, or aminoarene), theamine can comprise only one substituent located on the carbon atomadjacent to the ring carbon atom attached to the nitrogen atom of theamine group; or alternatively, the amine can comprise only onesubstituent located on each carbon atom adjacent to the ring carbon atomattached to the nitrogen atom of the amine group. In yet otherembodiments, when the nitrogen atom of the amine is attached to a ringatom (e.g. aminocycloalkane, aromatic amine, or aminoarene), the aminecan consist of only one substituent located on a carbon atom adjacent tothe ring carbon atom attached to the nitrogen atom of the amine group.

In an embodiment, the trihydrocarbylformate can have the formula(R^(f)O)₃CH. Generally, each R^(f) independently can be a C₁ to C₃₀hydrocarbyl group; alternatively, a C₁ to C₂₀ hydrocarbyl group;alternatively, a C₁ to C₁₅ hydrocarbyl group; alternatively, a C₁ to C₁₀hydrocarbyl group; or alternatively, a C₁ to C₅ hydrocarbyl group. Insome embodiments, each R^(f) independently can be C₆ to C₂₀ aromaticgroup; alternatively, a C₆ to C₁₅ aromatic group; alternatively, a C₆ toC₁₀ aromatic group; alternatively, a C₁ to C₂₀ alkyl group;alternatively, a C₁ to C₁₅ alkyl group; alternatively, a C₁ to C₁₀ alkylgroup; or alternatively, a C₁ to C₅ alkyl group. In some embodiments,each R^(f) independently can be a methyl group, an ethyl group, a propylgroup, a butyl group, or a phenyl group; alternatively, a methyl group;alternatively, an ethyl group; alternatively, a propyl group;alternatively, a butyl group; or alternatively, a phenyl group. In anembodiment, the trihydrocarbylformate can be trimethylformate,triethylformate, or triphenylformate; alternatively, trimethylformate;alternatively, triethylformate; or alternatively, triphenylformate.

In an embodiment, the acid catalyst can be any acid which can facilitatethe formation of the formamidine compound (or alternatively, thehydrocarboxymethanime compound). In an embodiment the acid catalyst cancomprise, consist essentially of, or consist of, an inorganic acid or anorganic acid; alternatively, an inorganic acid, or alternatively, anorganic acid. In certain embodiments, the organic acid can comprise,consist essentially of, or consist of, a C₁ to C₃₀ organic acid;alternatively, a C₁ to C₂₀ organic acid; alternatively, a C₁ to C₁₅organic acid; alternatively, a C₁ to C₁₀ organic acid; or alternatively,a C₁ to C₅ organic acid.

In an embodiment, the inorganic acid can comprise, consist essentiallyof, or consist of, hydrochloric acid, hydrobromic acid, hydroiodic acid,iodic acid, sulfuric acid, chlorosulfonic acid, sulfamic acid, nitricacid, phosphoric acid, meta-phosphoric acid, polyphorphoric acid,pyrophosphoric acid, fluorophosphoric acid, or any combination thereof.In some embodiments, the inorganic acid can comprise, consistessentially of, or consist of, hydrochloric acid, sulfuric acid, nitricacid, phosphoric acid, or any combination thereof; alternatively,hydrochloric acid; alternatively, hydrobromic acid; alternatively,hydroiodic acid; alternatively, iodic acid; alternatively, sulfuricacid; alternatively, chlorosulfonic acid; alternatively, sulfamic acid;alternatively, nitric acid; alternatively, phosphoric acid,alternatively, meta-phosphoric acid; alternatively, polyphorphoric acid;alternatively, pyrophosphoric acid; or alternatively, fluorophosphoricacid.

The organic acid can comprise, consist essentially of, or consist of, acarboxylic acid or an organic sulfonic acid; alternatively, a carboxylicacid; or alternatively, an organic sulfonic acid. Suitable carboxylicacids can have the same number of carbon atoms as the organic aciddisclosed herein. In an embodiment, the carboxylic acid can have thesame number of carbon atoms as the organic acid disclosed herein. In anembodiment, the organic sulfonic acid can have the same number of carbonatoms as the organic acid disclosed herein.

In an embodiment, the carboxylic acid can comprise, consist essentiallyof, or consist of formic acid, acetic acid, propionic acid, butyricacid, oxalic acid, trifluoroacetic acid, trichloroacetic acid, benzoicacid, a nitro substituted benzoic acid, a halo substituted benzoic acid,or any combination thereof; alternatively, trifluoroacetic acid; oralternatively, trichloroacetic acid. In an embodiment, the organicsulfonic acid can comprise, consist essentially of, or consist of anaryl sulfonic acid or an alkyl sulfonic acid; alternatively; an arylsulfonic acid; or alternatively, an alkyl sulfonic acid. In someembodiments, the aryl sulfonic acid can comprise, consist essentiallyof, or consist of benzene sulfonic acid, a substituted benzene sulfonicacid, naphthalene sulfonic acid, a substituted naphthalene sulfonicacid, or any combination thereof. Substituent groups are independentlydisclosed herein and can be utilized without limitation to furtherdescribe the substituted benzene sulfonic acid or substitutednaphthalene sulfonic acid which can be utilized as the acid catalyst. Insome embodiments, the organic sulfonic acid can comprise, consistessentially of, or consist of, methane sulfonic acid, benzene sulfonicacid, toluene sulfonic acid (ortho, meta, and/or para), dodecylbenzenesulfonic acid, naphthalene sulfonic acid, dinonylnaphthalene disulfonicacid, or any combination thereof; alternatively, methane sulfonic acid;alternatively, benzene sulfonic acid; or alternatively, toluene sulfonicacid (ortho, meta, and/or para).

In an embodiment, the formamidine compound can be utilized withoutfurther isolation or purification. In some embodiments, the formamidinecompound can be isolated; alternatively, purified; or alternatively,isolated and purified. In an embodiment, wherein the formamidinecompound can be prepared in a solvent, the method to prepare theformamidine compound can include a step of isolating the formamidinecompound by evaporating the solvent; or alternatively distilling thesolvent from the formamidine. In an embodiment wherein the formamidinecompound can be prepared in a solvent, the method to prepare theformamidine compound can include the step of isolating the formamidinecompound by filtering the solution to remove particulate materialsand/or byproducts of the reaction and evaporating the solvent (ordistilling the solvent) from the formamidine compound. In embodiments,the method to prepare the formamidine compound can include apurification step wherein the formamidine compound can be purified bydissolving the formamidine compound in a solvent and filtering thesolution to remove particulate materials and/or byproducts of thereaction. The solvent utilized to purify the formamidine compound can bethe same solvent utilized to form the formamidine compound or it can bedifferent than the solvent utilized to form the formamidine compound. Insome embodiments, the method to prepare the formamidine compound caninclude a purification step wherein the formamidine can be purified bywashing with a solvent. In other embodiments, the method to prepare theformamidine compound can include a purification step of recrystallizingthe formamidine compound.

In an embodiment, the hydrocarboxymethanimine compound can haveStructure HMA1.

R¹ within hydrocarboxymethanimine compound Structure HMA1 isindependently described as a feature of the N²-phosphinyl formamidinecompound Structures NPF1 and/or NPF2. Since the hydrocarboxymethaniminecompound HMA1 can be utilized to prepare embodiments of N²-phosphinylformamidine compounds having Structures NPF1 and/or NPF2, the R¹description for the N²-phosphinyl formamidine compounds can be utilizedwithout limitation to further describe the hydrocarboxymethaniminecompound Structure HMA1. R^(f) within the hydrocarboxymethanimine isdescribed as a feature of the trihydrocarbyl formate from which thehydrocarboxymethaninine is prepared. The R^(f) description for thetrihydrocarbylformates can be utilized without limitation to furtherdescribe the hydrocarboxymethanimine compound Structures HMA1.

In an embodiment, the hydrocarboxymethanimine compound can be utilizedwithout further isolation or purification. In some embodiments, thehydrocarboxymethanimine compound can be isolated; alternatively,purified; or alternatively, isolated and purified. In an embodiment,wherein the hydrocarboxymethanimine compound can be prepared in asolvent, the method to prepare the hydrocarboxymethanimine compound caninclude a step of isolating the hydrocarboxymethanimine compound byevaporating the solvent; or alternatively distilling the solvent fromthe hydrocarboxymethanimine compound. In an embodiment wherein thehydrocarboxymethanimine compound can be prepared in a solvent, themethod to prepare the hydrocarboxymethanimine compound can include thestep of isolating the hydrocarboxymethanimine compound by filtering thesolution to remove particulate materials and/or byproducts of thereaction and evaporating the solvent (or distilling the solvent) fromthe hydrocarboxymethanimine compound. In embodiments, the method toprepare the hydrocarboxymethanimine compound can include a purificationstep wherein the formamidine compound can be purified by dissolving thehydrocarboxymethanimine compound in a solvent and filtering the solutionto remove particulate materials and/or byproducts of the reaction. Thesolvent utilized to purify the hydrocarboxymethanimine compound can bethe same solvent utilized to form the hydrocarboxymethanimine compoundor it can be different than the solvent utilized to form thehydrocarboxymethanimine compound.

Ammonium compounds which can be utilized to form the formamidinecompound from a hydrocarboxymethanime can be any ammonium compound whichcan substitute an —NH₂ group for the hydrocarboxy group of thehydrocarboxymethanime compound. In an embodiment, the ammonium compoundcan be ammonium acetate, ammonium fluoride, ammonium chloride, ammoniumbromide, ammonium iodide, ammonium bicarbonate, ammonium carbonate,ammonium sulfate, ammonium bisulfate, ammonium phosphate, ammoniumnitrate, or any combination thereof; alternatively, ammonium acetate;alternatively, ammonium chloride; alternatively, ammonium carbonate;alternatively, ammonium sulfate, or alternatively, ammonium nitrate.

When an amine and a trihydrocarbylformate are combined to form aformamidine compound, the amine and the trihydrocarbylformate can becombined in an amine to metal compound equivalent ratio of at least1.8:1. In an embodiment, the amine and the trihydrocarbylformate can becombined in an amine to trihydrocarbylformate equivalent ratio of atleast 1.9:1; alternatively, of at least 1.95:1; or alternatively, of atleast 1.98:1. In some embodiments, the amine and thetrihydrocarbylformate can be combined in an amine totrihydrocarbylformate equivalent ratio ranging from 1.8:1 to 2.5:1;alternatively, ranging from 1.9:1 to 2.4:1; alternatively, ranging from1.95:1 to 2.3:1; or alternatively, ranging from 1.98:1 to 2.2:1. Inother embodiments, the amine and the trihydrocarbylformate can becombined in an amine to trihydrocarbylformate equivalent ratio of about2:1.

When an amine and a trihydrocarbylformate are combined to form ahydrocarboxymethanimine compound, the amine and thetrihydrocarbylformate can be combined in an amine to metal compoundequivalent ratio of at least 0.25:1. In an embodiment, the amine and thetrihydrocarbylformate can be combined in an amine totrihydrocarbylformate equivalent ratio of at least 0.35:1;alternatively, of at least 0.4:1; or alternatively, of at least 0.45:1.In some embodiments, the amine and the trihydrocarbylformate can becombined in an amine to trihydrocarbylformate equivalent ratio rangingfrom 0.25:1 to 0.75:1; alternatively, ranging from 0.35:1 to 0.7:1;alternatively, ranging from 0.4:1 to 0.6:1; or alternatively, rangingfrom 0.45:1 to 0.55:1. In other embodiments, the amine and thetrihydrocarbylformate can be combined in an amine totrihydrocarbylformate equivalent ratio of about 0.5:1.

In an embodiment where an amine and a trihydrocarbylformate are combinedto form a hydrocarboxymethanime compound or a formamidine compound, theconditions capable of forming the hydrocarboxymethanime compound or theformamidine compound can include a temperature of at least 0° C.;alternatively, of at least 15° C.; alternatively, of at least 25° C.; oralternatively, of at least 40° C. In some embodiments where an amine anda trihydrocarbylformate are combined to form a hydrocarboxymethanimecompound or a formamidine compound, the conditions capable of formingthe hydrocarboxymethanime compound or a formamidine compound can includea temperature ranging from 0° C. to 200° C.; alternatively, ranging from15° C. to 175° C.; alternatively, ranging from 25° C. to 150° C.; oralternatively, ranging from 40° C. to 125° C.

In an embodiment where an amine and a trihydrocarbylformate are combinedto form a hydrocarboxymethanime compound or a formamidine compound, theconditions capable of forming the hydrocarboxymethanime compound or theformamidine compound can include a hydrocarboxymethanime compound or aformamidine compound formation time of at least 5 minutes;alternatively, of at least 30 minutes; alternatively, of at least 45minutes; or alternatively, of at least 1 hour. In some embodiments wherean amine and a trihydrocarbylformate are combined to form ahydrocarboxymethanime compound or a formamidine compound, the conditionscapable of forming the hydrocarboxymethanime compound or the formamidinecompound can include a hydrocarboxymethanime compound or a formamidinecompound formation time ranging from 5 minutes to 48 hours;alternatively, ranging from 30 minutes to 36 hours; alternatively,ranging from 45 minutes to 30 hours; or alternatively, ranging from 1hour to 24 hours.

In an embodiment where an amine and a trihydrocarbylformate are combinedto form a hydrocarboxymethanime compound or a formamidine compound, thehydrocarboxymethanime compound or a formamidine compound can be formedin an aprotic solvent (or the amine and the trihydrocarbylformate can becontacted with an aprotic solvent). In some embodiments, the amine andthe trihydrocarbylformate can be contacted in a polar aprotic solvent.Aprotic solvents which can be utilized include hydrocarbon solvents andether solvents. Polar aprotic solvents which can be utilized includeether solvents. Solvents are generally disclosed herein and any generalor specific aprotic solvent and/or polar aprotic solvent describedherein can be utilized to further describe the method of preparing thehydrocarboxymethanime compound or a formamidine compound.

When a hydrocarboxylmethanime compound and an ammonium compound arecombined to form a formamidine compound, the hydrocarboxylmethanimecompound and the ammonium compound can be combined at an ammoniumcompound to hydrocarboxylmethanime compound equivalent ratio of at least0.25:1. In an embodiment, the ammonium compound and thehydrocarboxylmethanime compound can be combined at an ammonium compoundto hydrocarboxylmethanime compound equivalent ratio of at least 0.35:1;alternatively, of at least 0.4:1; or alternatively, of at least 0.45:1.In some embodiments, the ammonium compound and thehydrocarboxylmethanime compound can be combined at an ammonium compoundto hydrocarboxylmethanime compound equivalent ratio ranging from 0.25:1to 0.75:1; alternatively, ranging from 0.35:1 to 0.7:1; alternatively,ranging from 0.4:1 to 0.6:1; or alternatively, ranging from 0.45:1 to0.55:1. In other embodiments, the ammonium compound and thehydrocarboxylmethanime compound can be combined at an ammonium compoundto hydrocarboxylmethanime compound equivalent ratio of about 0.5:1.

In an embodiment where a hydrocarboxylmethanime compound and an ammoniumcompound are combined to form a formamidine compound, the conditionscapable of forming the formamidine compound can include a temperature ofat least 0° C.; alternatively, of at least 5° C.; alternatively, of atleast 10° C.; or alternatively, of at least 15° C. In some embodimentswhere an amine and a trihydrocarbylformate are combined to form aformamidine compound, the conditions capable of forming the formamidinecompound can include a temperature ranging from 0° C. to 60° C.;alternatively, ranging from 5° C. to 50° C.; alternatively, ranging from10° C. to 45° C.; or alternatively, ranging from 15° C. to 40° C. Insome embodiments where an amine and a trihydrocarbylformate are combinedto form a formamidine compound, the conditions capable of forming theformamidine compound can include forming the formamidine compound atabout ambient temperature.

In an embodiment where a hydrocarboxylmethanime compound and an ammoniumcompound are combined to form a formamidine compound, the conditionscapable of forming the formamidine compound can include a formamidinecompound formation time of at least 5 minutes; alternatively, of atleast 30 minutes; alternatively, of at least 45 minutes; oralternatively, of at least 1 hour. In some embodiments where ahydrocarboxylmethanime compound and an ammonium compound are combined toform a formamidine compound, the conditions capable of forming theformamidine compound can include a formamidine compound formation timeranging from 5 minutes to 48 hours; alternatively, ranging from 30minutes to 36 hours; alternatively, ranging from 45 minutes to 30 hours;or alternatively, ranging from 1 hour to 24 hours.

In an embodiment where a hydrocarboxylmethanime compound and an ammoniumcompound are combined to form a formamidine compound, the formamidinecompound can be formed in a polar solvent (or the hydrocarboxymethanimecompound and the ammonium compound can be contacted with a polarsolvent). In some embodiments, the hydrocarboxylmethanime compound andthe ammonium compound can be contacted with polar aprotic solvent; oralternatively, a polar protic solvent. Solvents are generally disclosedherein and any general or specific polar aprotic solvent and/or polarprotic solvent described herein can be utilized to further describe themethod of preparing the formamidine compound by contacting ahydrocarboxylmethanime compound and an ammonium compound.

Evaporation of the solvent, regardless of whether it is performed toseparate 1) the formamidine compound from the solvent in the preparationof the formamidine compound by contacting an amine and atrihydrocarbylformate, 2) the hydrocarboxymethanime compound from thesolvent in the preparation of the hydrocarboxymethanimine compound bycontacting an amine and a trihydrocarbylformate, and/or 3) theformamidine compound from the solvent in the preparation of theformamidine compound by contacting a hydrocarboxymethanimine compoundand an ammonium compound can be performed using any suitable method. Inan embodiment, the solvent can be evaporated at ambient temperature(15-35° C.—no applied external heat source); alternatively, the solventcan be evaporated with gentle heating (e.g., at a temperature rangingfrom 25° C. to 50° C.); alternatively, the solvent can be evaporated atambient temperature under reduced pressure; or alternatively, thesolvent can be evaporated with gentle heating under reduced pressure.Distilling the solvent from the formamidine (or thehydrocarboxymethanimine) can be performed using any suitable method. Inan embodiment, the distillation can be performed at ambient pressure; oralternatively, the distillation can be performed under reduced pressure.In some embodiments, the distillation can be utilized to separate othermaterials (e.g., excess amine utilized in the synthesis, and/orimpurities formed during the synthesis, among other things) from theformamidine compound and/or the hydrocarboxymethanimine compound.

Methods of preparing a formamidine compound by contacting an amine and atrihydrocarbylformate to form a formamidine compound can produce aformamidine compound having Structure FA1 having the same group for R¹and R³. Methods of preparing a formamidine compound by contacting ahydrocarboxymethanimine compound and an ammonium compound to form aformamidine compound produce formamidine compounds having two N²hydrogens (e.g., formamidine compounds having Structure FA2). However,in some instances it may be desirable to have N²-phosphinyl formamidinecompounds having a non-hydrogen R³ N² group which is different than theR¹ group; e.g., N²-phosphinyl formamidine compounds having StructuresNPF1 (where R¹ and R³ are different). Two methods of preparing theN²-phosphinyl formamidine compounds having a non-hydrogen R³ N² groupwhich is different than the R¹ group include: a) alkylating aformamidine compound having two N² hydrogen atoms (e.g., a formamidinecompound having Structure FA2) to produce a formamidine compound havingStructures FA1 wherein R³ is an non-hydrogen group and converting theformamidine compound to an N²-phosphinyl formamidine compound (e.g.,N²-phosphinyl formamidine compounds having Structure NPF1) utilizingmethods described herein and b) alkylating an N²-phosphinyl formamidinecompound having an N² hydrogen atom (e.g., an N²-phosphinyl formamidinecompound having Structure NPF2).

Alkylation of Formamidine Compounds

In an aspect, a method of alkylating a formamidine compound cancomprise: a) contacting a first formamidine compound having an N²hydrogen atom and a metallic compound capable of abstracting a protonfrom a —NH₂ group or a >NH group; b) forming a metal formamidinate; c)contacting a halogenated compound with the metal formamidinate and d)forming a second formamidine compound. Generally, the metalformamidinate can be formed under conditions capable of forming a metalformamidinate. In an embodiment, the metal formamidinate can beisolated; alternatively, purified; or alternatively, isolated andpurified. Generally, the second formamidine compound can be formed underconditions capable of forming a formamidine compound. In an embodiment,the second formamidine compound can be isolated; alternatively,purified; or alternatively, isolated and purified. Methods steps,metallic compounds capable of abstracting a proton from a —NH₂ group ora >NH group, and method conditions for preparing metal formamidinatesare described herein and can be utilized without limitation to furtherdescribe the method for alkylating a formamidine compound.

Generally, the halogenated compound and the metal formamidinate can becombined in a halogenated compound to metal formamidinate equivalentratio of at least 0.9:1. In some embodiments, the halogenated compoundand the metal formamidinate can be combined in a halogenated compound tometal formamidinate equivalent ratio of at least 0.95:1; alternatively,at least 0.975:1; or alternatively, at least 0.99:1. In someembodiments, the halogenated compound and the metal formamidinate can becombined in a halogenated compound to metal formamidinate equivalentratio ranging from 0.9:1 to 1.25:1; alternatively, ranging from 0.95:1to 1.20:1; alternatively, ranging from 0.975:1 to 1.15:1; oralternatively, ranging from 0.99:1 to 1.10:1. In other embodiments, thehalogenated compound and the metal formamidinate can be combined in ahalogenated compound to metal formamidinate equivalent ratio of about1:1.

In an embodiment, the conditions capable of forming the secondformamidine compound can include a reaction temperature of at least 0°C.; alternatively, of at least 5° C.; alternatively, of at least 10° C.;or alternatively, of at least 15° C. In some embodiments, the conditionscapable of forming the second formamidine compound can include areaction temperature ranging from 0° C. to 60° C.; alternatively,ranging from 5° C. to 50° C.; alternatively, ranging from 10° C. to 45°C.; or alternatively, ranging from 15° C. to 40° C. In an embodiment,the conditions capable of forming the second formamidine compound caninclude a reaction time of at least 5 minutes; alternatively, of atleast 10 minutes; alternatively, of at least 15 minutes; oralternatively, of at least 20 minutes. In some embodiments, theconditions capable of forming the second formamidine compound caninclude a reaction time ranging from 5 minutes to 6 hours;alternatively, ranging from 10 minutes to 5 hours; alternatively,ranging from 15 minutes to 4.5 hours; or alternatively, ranging from 20minutes to 4 hours.

In an embodiment, the halogenated compound and the metal formamidinatecan be contacted in an aprotic solvent. In some embodiments, thehalogenated compound and the metal formamidinate can be contacted in apolar aprotic solvent. Aprotic solvents which can be utilized includehydrocarbon solvents and ether solvents. Polar aprotic solvents whichcan be utilized include ether solvents. Solvents are generally disclosedherein and any general or specific aprotic solvent and/or polar aproticsolvent described herein can be utilized to further describe the methodof preparing a formamidine compound comprising contacting a halogenatedcompound with a metal formamidinate and forming the formamidinecompound.

In an embodiment, the second formamidine compound can be utilizedwithout further isolation or purification. In some embodiments, thesecond formamidine compound can be isolated; alternatively, purified; oralternatively isolated and purified. In an embodiment, wherein thesecond formamidine compound can be prepared in a solvent (aprotic orpolar aprotic), the method to alkylate a formamidine compound caninclude a step of isolating the second formamidine compound byevaporating the solvent. In an embodiment wherein the second formamidinecompound can be prepared in a solvent (aprotic or polar aprotic), themethod to alkylate a second formamidine compound can include the step ofisolating the second formamidine compound by filtering the solution toremove particulate materials and/or byproducts of the reaction andevaporating the solvent. In embodiments, the method to alkylate aformamidine compound can include a purification step wherein the secondformamidine compound can purified by dissolving the second formamidinecompound in a solvent and filtering the solution to remove particulatematerials and/or byproducts of the reaction. The solvent utilized topurify the second formamidine compound can be the same as the solventutilized to form the second formamidine compound or it can be differentthan the solvent utilized to form the second formamidine compound. Insome embodiments, the method to alkylate a formamidine compound caninclude purifying the second formamidine compound by washing the secondformamidine compound with a solvent. In other embodiments, the method toalkylate a formamidine compound can include recrystallizing the secondformamidine compound.

Generally, evaporation of the solvent can be performed using anysuitable method. In some embodiments, the solvent can be evaporated atambient temperature (15-35° C.—no applied external heat source). Inother embodiments, the solvent can be evaporated with gentle heating(e.g., at a temperature ranging from 25° C. to 50° C.). In furtherembodiments, the solvent can be evaporated at ambient temperature underreduced pressure. In yet other embodiments, the solvent can beevaporated with gentle heating under reduced pressure.

Alkylation of N²-Phosphinyl Formamidine Compounds

In an aspect, a method of alkylating an N²-phosphinyl formamidinecompound can comprise: a) contacting an N²-phosphinyl formamidinecompound having an N² hydrogen and a metallic compound capable ofabstracting a proton from a —NH₂ group or a >NH group; b) forming ametal N²-phosphinyl formamidinate; c) contacting a halogenated compoundwith the metal N²-phosphinyl formamidinate and d) forming a secondN²-phosphinyl formamidine compound. Generally, the metal formamidinatecan be formed under conditions capable of forming a metal formamidinate.In an embodiment, the metal N²-phosphinyl formamidinate can be isolated;alternatively, purified; or alternatively, isolated and purified.Generally, the second N²-phosphinyl formamidine compound can be formedunder conditions capable of forming the second N²-phosphinyl formamidinecompound. In an embodiment, the second N²-phosphinyl formamidinecompound can be isolated; alternatively, purified; or alternatively,isolated and purified.

In an embodiment, the N²-phosphinyl formamidine compound having an N²hydrogen can have Structure NPF2. In an embodiment, the secondN²-phosphinyl formamidine compound can have Structure NPF1.N²-phosphinyl formamidine compounds having Structure NPF1 and NPF2 aredescribed herein. These N²-phosphinyl formamidine compounds can beutilized without limitation to further describe the method of alkylatingan N²-phosphinyl formamide compound.

In an embodiment, the metallic compound capable of abstracting a protonfrom a —NH₂ group or a >NH group are described herein (e.g., withinmethods for preparing metal formamidinates). These metallic compoundscapable of abstracting a proton from a —NH₂ group or a >NH group can beutilized, without limitation, to further describe the method ofalkylating an N²-phosphinyl formamidine compound.

Generally, the first N²-phosphinyl formamidine compound and the metalliccompound capable of abstracting a proton from a —NH₂ group or a >NHgroup can be combined in an N²-phosphinyl formamidine compound tometallic compound equivalent ratio of at least 0.9:1. In an embodiment,the N²-phosphinyl formamidine compound and the metallic compound capableof abstracting a proton from a —NH₂ group or a >NH group can be combinedin an N²-phosphinyl formamidine compound to metallic compound equivalentratio of at least 0.95:1; alternatively, of at least 0.975:1; oralternatively, of at least 0.99:1. In some embodiments, theN²-phosphinyl formamidine compound and the metallic compound capable ofabstracting a proton from a —NH₂ group or a >NH group can be combined inan N²-phosphinyl formamidine compound and metallic compound equivalentratio ranging from 0.9:1 to 1.25:1; alternatively, ranging from 0.95:1to 1.20:1; alternatively, ranging from 0.975:1 to 1.15:1; oralternatively, ranging from 0.99:1 to 1.10:1. In other embodiments, theN²-phosphinyl formamidine compound and the metallic compound capable ofabstracting a proton from a —NH₂ group or a >NH group can be combined inan N²-phosphinyl formamidine compound to metallic compound equivalentratio of about 1:1.

In an embodiment, the conditions capable of forming the metalN²-phosphinyl formamidinate can include a temperature of at least −45°C.; alternatively, of at least −30° C.; alternatively, of at least −25°C.; or alternatively, of at least −20° C. In some embodiments, thereaction conditions capable of forming a metal N²-phosphinylformamidinate can include a temperature ranging from −45° C. to 60° C.;alternatively, ranging from −30° C. to 50° C.; alternatively, rangingfrom −25° C. to 45° C.; or alternatively, ranging from −20° C. to 40° C.

In some embodiments, the conditions capable of forming the metalN²-phosphinyl formamidinate can include an initial metallic compoundcapable of abstracting a proton from a —NH₂ group or a >NH group andfirst N²-phosphinyl formamidine contact temperature and a secondtemperature to form the metal N²-phosphinyl formamidinate. It should benoted the when the conditions capable of forming the metal N²-phosphinylformamidinate is described as occurring at two temperatures (one for thecontact of the metallic compound capable of abstracting a proton from a—NH₂ group or a >NH group and the first N²-phosphinyl formamidine andone for the formation of the metal N²-phosphinyl formamidinate) thatthis description does not exclude the prospect that metal N²-phosphinylformamidinate can be formed at the contact temperature. The descriptionjust relates that, in some embodiments, the metal N²-phosphinylformamidinate formation can proceed better when the initial contactbetween the metallic compound capable of abstracting a proton from a—NH₂ group or a >NH group and first N²-phosphinyl formamidine compoundis performed at one temperature and the formation of the metalN²-phosphinyl formamidinate is completed at a second differenttemperature.

In an embodiment, the metallic compound capable of abstracting a protonfrom a —NH₂ group or a >NH group and the first N²-phosphinyl formamidinecan be contacted at a temperature ranging from −45° C. to 20° C.;alternatively, ranging from −30° C. to 15° C.; alternatively, rangingfrom −25° C. to 45° C.; or alternatively, ranging from −20° C. to 40° C.In an embodiment, metal N²-phosphinyl formamidinate can be formed at atemperature ranging from 0° C. to 20° C.; alternatively, ranging from 5°C. to 15° C.; alternatively, ranging from 10° C. to 45° C.; oralternatively, ranging from 15° C. to 40° C.

In an embodiment, the conditions capable of forming the metalN²-phosphinyl formamidinate can include a metal N²-phosphinylformamidinate formation time of at least 5 minutes; alternatively, of atleast 10 minutes; alternatively, of at least 15 minutes; oralternatively, of at least 20 minutes. In some embodiments, theconditions capable of forming the metal N²-phosphinyl formamidinate caninclude a metal N²-phosphinyl formamidinate formation time ranging from5 minutes to 6 hours; alternatively, ranging from 10 minutes to 5 hours;alternatively, ranging from 15 minutes to 4.5 hours; or alternatively,ranging from 20 minutes to 4 hours.

In an embodiment, the metallic compound capable of abstracting a protonfrom a —NH₂ group or a >NH group and the N²-phosphinyl formamidinecompound can be contacted in an aprotic solvent. In some embodiments,the metallic compound capable of abstracting a proton from a —NH₂ groupor a >NH group and the N²-phosphinyl formamidine compound can becontacted in a polar aprotic solvent. Aprotic solvents which can beutilized include hydrocarbon solvents and ether solvents. Polar aproticsolvents which can be utilized include ether solvents. Solvents aregenerally disclosed herein and any general or specific aprotic solventand/or polar aprotic solvent described herein can be utilized to furtherdescribe the method of preparing the metal N²-phosphinyl formamidinateby contacting a metallic compound capable of abstracting a proton from a—NH₂ group or a >NH group and an N²-phosphinyl formamidine compound andforming a metal N²-phosphinyl formamidinate.

In an embodiment, the metal N²-phosphinyl formamidinate can be utilizedwithout further isolation or purification. In some embodiments, themetal N²-phosphinyl formamidinate can be isolated; alternatively,purified; or alternatively isolated and purified. In an embodiment, themethod can include a step of isolating the metal N²-phosphinylformamidinate by filtering the metal N²-phosphinyl formamidinate fromthe solution. In some embodiments, the method can include a step ofpurifying the metal N²-phosphinyl formamidinate by washing the metalN²-phosphinyl formamidinate with a solvent. Generally, the washingsolvent is an aprotic solvent. In other embodiments, the washing solventcan be polar aprotic solvent. In other embodiments, the washing solventcan be a non-polar aprotic solvent.

In an embodiment, the halogenated compound can have Structure HC1. Thehalogenated compounds which can be utilized to alkylate a formamidinecompound (via a reaction with a metal formamidinate) are the samehalogenated compounds which can be utilized to alkylate an N²-phosphinylformamidine compound (via a reaction with a metal N²-phosphinylformamidinate). These halogenated compounds are disclosed herein and canbe utilized, without limitation, to further describe the method toalkylate an N²-phosphinyl formamidine compound.

Generally, the halogenated compound and the metal N²-phosphinylformamidinate can be combined in a halogenated compound to metalN²-phosphinyl formamidinate equivalent ratio of at least 0.9:1. In someembodiments, the halogenated compound and the metal N²-phosphinylformamidinate can be combined in a halogenated compound to metalN²-phosphinyl formamidinate equivalent ratio of at least 0.95:1;alternatively, of at least 0.975:1; or alternatively, of at least0.99:1. In some embodiments, the halogenated compound and the metalN²-phosphinyl formamidinate can be combined in a halogenated compound tometal N²-phosphinyl formamidinate equivalent ratio ranging from 0.9:1 to1.25:1; alternatively, ranging from 0.95:1 to 1.20:1; alternatively,ranging from 0.975:1 to 1.15:1; or alternatively, ranging from 0.99:1 to1.10:1. In other embodiments, the halogenated compound and the metalN²-phosphinyl formamidinate can be combined in a halogenated compound tometal N²-phosphinyl formamidinate equivalent ratio of about 1:1.

In an embodiment, conditions capable of forming the second N²-phosphinylformamidine compound can include a reaction temperature of at least 0°C.; alternatively, of at least 5° C.; alternatively, of at least 10° C.;or alternatively, of at least 15° C. In some embodiments, conditionscapable of forming the second N²-phosphinyl formamidine compound caninclude a reaction temperature ranging from 0° C. to 60° C.;alternatively, ranging from 5° C. to 50° C.; alternatively, ranging from10° C. to 45° C.; or alternatively, ranging from 15° C. to 40° C. In anembodiment, conditions capable of forming the second N²-phosphinylformamidine compound can include a reaction time of at least 5 minutes;alternatively, of at least 10 minutes; alternatively, of at least 15minutes; or alternatively, of at least 20 minutes. In some embodiments,conditions capable of forming the second N²-phosphinyl formamidinecompound can include a reaction time ranging from 5 minutes to 6 hours;alternatively, ranging from 10 minutes to 5 hours; alternatively,ranging from 15 minutes to 4.5 hours; or alternatively, ranging from 20minutes to 4 hours.

In an embodiment, the halogenated compound and the metal N²-phosphinylformamidinate can be contacted in an aprotic solvent. In someembodiments, the halogenated compound and the metal N²-phosphinylformamidinate can be contacted in a polar aprotic solvent. Aproticsolvents which can be utilized include hydrocarbon solvents and ethersolvents. Polar aprotic solvents which can be utilized include ethersolvents. Solvents are generally disclosed herein and any general orspecific aprotic solvent and/or polar aprotic solvent described hereincan be utilized to further describe the method of preparing anN²-phosphinyl formamidine compound comprising contacting a halogenatedcompound with a metal N²-phosphinyl formamidinate and forming theN²-phosphinyl formamidinate.

In an embodiment, the second N²-phosphinyl formamidine compound can beutilized without further isolation or purification. In some embodiments,the second N²-phosphinyl formamidine compound can be isolated;alternatively, purified; or alternatively isolated and purified. In anembodiment, wherein the second N²-phosphinyl formamidine compound isprepared in a solvent (aprotic or polar aprotic), the method to alkylatethe N²-phosphinyl formamidine compound can include a step of isolatingthe second N²-phosphinyl formamidine compound by evaporating thesolvent. In an embodiment wherein the second N²-phosphinyl formamidinecompound is prepared in a solvent (aprotic or polar aprotic), the methodto alkylate an N²-phosphinyl formamidine compound can include the stepof isolating the second N²-phosphinyl formamidine compound by filteringthe solution to remove particulate materials and/or byproducts of thereaction and evaporating the solvent. In embodiments, the method toalkylate an N²-phosphinyl formamidine compound can include apurification step wherein the second N²-phosphinyl formamidine compoundis purified by dissolving the second N²-phosphinyl formamidine compoundin a solvent and filtering the solution to remove particulate materialsand/or byproducts of the reaction. The solvent utilized to purify thesecond N²-phosphinyl formamidine compound can be the same as the solventutilized to form the second N²-phosphinyl formamidine compound or it canbe different than the solvent utilized to form the second N²-phosphinylformamidine compound. In some embodiments, the method to alkylate anN²-phosphinyl formamidine compound can include purifying the secondN²-phosphinyl formamidine compound by washing the second N²-phosphinylformamidine compound with a solvent. In other embodiments, the method toalkylate an N²-phosphinyl formamidine compound can include arecrystallizing the second N²-phosphinyl formamidine compound.

Generally, evaporation of the solvent can be performed using anysuitable method. In some embodiments, the solvent can be evaporated atambient temperature (15-35° C.—no applied external heat source). Inother embodiments, the solvent can be evaporated with gentle heating(e.g. at a temperature ranging from 25° C. to 50° C.). In furtherembodiments, the solvent can be evaporated at ambient temperature underreduced pressure. In yet other embodiments, the solvent can beevaporated with gentle heating under reduced pressure.

In an embodiment, the halogenated compound which can be utilized in thealkylation of the formamidine compounds or in the alkylation of theN²-phosphinyl formamidine compounds can have Structure HC1.X²R³  Structure HC1X² of Structure HC1 represents a halide. In an embodiment, X² of thehalogenated compound can be fluoride, chloride, bromide, or iodide;alternatively, fluoride; alternatively, chloride; alternatively,bromide; or alternatively, iodide. R³ within halogenated compoundStructure HC1 is independently described as a feature of theN²-phosphinyl formamidine compounds having Structure NPF1. Sincehalogenated compound HC1 is utilized to prepare embodiments ofN²-phosphinyl formamidine compounds having Structure NPF1, the R³description for the N²-phosphinyl formamidine compounds can be utilizedwithout limitation to further describe halogenated compounds havingStructure HC1. Halogenated compounds are disclosed herein and can beutilized, without limitation, to further describe the method to alkylatea formamidine compound or in the alkylation of the N²-phosphinylformamidine compounds.

In an aspect, the halogenated compound having Structure HC1 can be amethylhalide, an ethylhalide, a propylhalide, a butylhalide, apentylhalide, a hexylhalide, a heptylhalide, an octylhalide, anonylhalide, a decylhalide, a undecylhalide, a dodecylhalide, atridecylhalide, a tetradecylhalide, a pentadecylhalide, ahexadecylhalide, a heptadecylhalide, an octadecylhalide, or anonadecylhalide; or alternatively, a methylhalide, an ethylhalide, apropylhalide, a butylhalide, a pentylhalide, a hexylhalide, aheptylhalide, an octylhalide, a nonylhalide, or a decylhalide. In someembodiments, the halogenated compound having Structure HC1 can be amethylhalide, an ethylhalide, an n-propylhalide, an iso-propylhalide,butylhalide, an iso-butylhalide, a sec-butylhalide, a tert-butylhalide,an n-pentylhalide, an iso-pentylhalide, a sec-pentylhalide, or anneopentylhalide; alternatively, a methylhalide, an ethylhalide, aniso-propylhalide, a tert-butylhalide, or a neopentylhalide;alternatively, a methylhalide; alternatively, an ethylhalide;alternatively, an n-propylhalide; alternatively, an iso-propylhalide;alternatively, a tert-butylhalide; or alternatively, a neopentylhalide.

In an aspect, the halogenated compound having Structure HC1 can be acyclobutylhalide, a substituted cyclobutylhalide, a cyclopentylhalide, asubstituted cyclopentylhalide, a cyclohexylhalide, a substitutedcyclohexylhalide, a cycloheptylhalide, a substituted cycloheptylhalide,a cyclooctylhalide, or a substituted cyclooctylhalide. In an embodimentthe halide having Structure HC1 can be a cyclopentylhalide, asubstituted cyclopentylhalide, a cyclohexylhalide, or a substitutedcyclohexylhalide. In other embodiments, the halogenated compound havingStructure HC1 can be a cyclopentylhalide or a substitutedcyclopentylhalide; or alternatively, a cyclohexylhalide or a substitutedcyclohexylhalide. In further embodiments, the halogenated compoundhaving Structure HC1 can be a cyclopentylhalide; alternatively, asubstituted cyclopentylhalide; a cyclohexylhalide; or alternatively, asubstituted cyclohexylhalide. Substituents and substituents patterns forthe R¹ cycloalkyl groups are described herein and can be utilizedwithout limitation to further describe the substituted cycloalkylhalideswhich can be utilized in aspects and embodiments described herein.

In various embodiments, the halogenated compounds which can be utilizedcan have Structure HC2. R^(31c), R^(32c), R^(33c), R^(34c), and R^(35c)substituents, substituent patterns, and n for the R³ group having

Structure G5 are described herein and can be utilized without limitationto describe halogenated compound having Structure HC2 which can beutilized in the various aspects and/or embodiments described herein. Inan embodiment, X² of the halogenated compound having Structure HC2 canbe fluoride, chloride, bromide, or iodide; alternatively, fluoride;alternatively, chloride; alternatively, bromide; or alternatively,iodide.

In an aspect, the halogenated compound can be a benzylhalide or asubstituted benzylhalide. In an embodiment, the halogenated compound canbe a benzylhalide; or alternatively, a substituted benzyl halide.

Generally, the method of preparing the formamidine compound, the methodof preparing the metal formamidinate, and the N²-phosphinyl formamidinecompound can be combined in various embodiments to provide additionalmethods of forming an N²-phosphinyl formamidine compound having only oneN² hydrogen atom utilizing amines, trihydrocarboxyformates, compoundscapable of abstracting a proton from a —NH₂ group or a >NH group,alkylating compounds, and phosphine halide. In a non-limitingembodiment, a method of preparing an N²-phosphinyl formamidine compoundcan comprise, consist essentially of, or consist of: a) contacting anamine and a trihydrocarbylformate; b) forming the formamidine compound;c) contacting the formamidine compound and a metallic compound capableof abstracting a proton from a —NH₂ group or a >NH group; d) forming ametal formamidinate; e) contacting the metal formamidinate with aphosphine halide; and f) forming an N²-phosphinyl formamidine compound.In another non-limiting embodiment, a method of preparing anN²-phosphinyl formamidine compound can comprise, consist essentially of,or consist of: a) contacting an amine and a trihydrocarbylformate; b)forming a hydrocarboxymethanimine compound; c) contacting thehydrocarboxymethanimine compound and an ammonium compound; d) formingthe formamidine compound; e) contacting the formamidine compound and ametallic compound capable of abstracting a proton from a —NH₂ group ora >NH group; 0 forming a metal formamidinate; g) contacting the metalformamidinate with a phosphine halide; and h) forming an N²-phosphinylformamidine compound. In yet another non-limiting embodiment, a methodof preparing an N²-phosphinyl formamidine compound can comprise, consistessentially of, or consist of: a) contacting an amine and atrihydrocarbylformate; b) forming a hydrocarboxymethanimine compound; c)contacting the hydrocarboxymethanimine compound and an ammoniumcompound; d) forming the formamidine compound; e) contacting theformamidine compound and a metallic compound capable of abstracting aproton from a —NH₂ group or a >NH group; f) forming a metalformamidinate; g) contacting the metal formamidinate with a halogenatedcompound; h) forming a second formamidine compound; i) contacting thesecond formamidine compound and a metallic compound capable ofabstracting a proton from a —NH₂ group or a >NH group; j) forming asecond metal formamidinate; k) contacting the second metal formamidinatewith a phosphine halide; and l) forming an N²-phosphinyl formamidinecompound. In a further non-limiting embodiment, a method of preparing anN²-phosphinyl formamidine compound can comprise, consist essentially of,or consist of: a) contacting an amine and a trihydrocarbylformate; b)forming a hydrocarboxymethanimine compound; c) contacting thehydrocarboxymethanimine compound and an ammonium compound; d) formingthe formamidine compound; e) contacting the formamidine compound and ametallic compound capable of abstracting a proton from a —NH₂ group ora >NH group; 0 forming a metal formamidinate; g) contacting the metalformamidinate with a phosphine halide; h) forming an N²-phosphinylformamidine compound; i) contacting the N²-phosphinyl formamidinecompound and a metallic compound capable of abstracting a proton from a—NH₂ group or a >NH group; j) forming a metal N²-phosphinylformamidinate; k) contacting the metal N²-phosphinyl formamidinate witha halogenated compound; and 1) forming a second N²-phosphinylformamidine compound. These methods can contain additional stepsdisclosed herein and/or features (e.g. reagent ratios, formationconditions, among other considerations) are described herein. It shouldbe noted that when additional steps are included in the methodsappropriate step identifiers (e.g. 1), 2), etc. . . . , a), b), etc. . .. , or i), ii), etc. . . . ) and compound/solvent identifiers (e.g.first, second, etc. . . . ) can be added and/or modified to indicateindividual and/or different steps/compounds/solvents utilized within thepreparation of the N²-phosphinyl formamidine compound without detractingfrom the general disclosure.

Method of Preparing N²-Phosphinyl Formamidine Metal Salt Complexes

In an aspect, this disclosure relates to a method of preparing anN²-phosphinyl formamidine metal salt complex. Generally, the method ofpreparing the N²-phosphinyl formamidine metal salt complex can comprise:a) contacting a metal salt with an N²-phosphinyl formamidine compound;and b) forming the N²-phosphinyl formamidine metal salt complex.Generally, the N²-phosphinyl formamidine metal salt complex can beformed under conditions capable of forming an N²-phosphinyl formamidinemetal salt complex. In some embodiments, the N²-phosphinyl formamidinemetal salt complex can be isolated; alternatively purified; oralternatively, isolated and purified.

N²-phosphinyl formamidine compounds are disclosed herein and can beutilized without limitation to further describe the method of preparingan N²-phosphinyl formamidine metal salt complex. Metal salts aredisclosed herein and can be utilized without limitation to furtherdescribe the method of preparing an N²-phosphinyl formamidine metal saltcomplex.

Generally, the metal salt and the N²-phosphinyl formamidine compound canbe contacted at a metal salt to N²-phosphinyl formamidine compoundequivalent ratio of at least 0.9:1. In some embodiments, the metal saltand the N²-phosphinyl formamidine compound can be contacted at a metalsalt to N²-phosphinyl formamidine compound equivalent ratio of at least0.95:1; alternatively, of at least 0.975:1; or alternatively, of atleast 0.99:1. In some embodiments, the metal salt and the N²-phosphinylformamidine compound can be contacted at a metal salt to N²-phosphinylformamidine compound equivalent ratio ranging from 0.9:1 to 1.25:1;alternatively, ranging from 0.95:1 to 1.20:1; alternatively, rangingfrom 0.975:1 to 1.15:1; or alternatively, ranging from 0.99:1 to 1.10:1.In other embodiments, the metal salt and the N²-phosphinyl formamidinecompound can be contacted at a metal salt to N²-phosphinyl formamidinecompound equivalent ratio of about 1:1.

In an embodiment, conditions capable of forming an N²-phosphinylformamidine metal salt complex can include a contact temperature of atleast 0° C.; alternatively, of at least 5° C.; alternatively, of atleast 10° C.; or alternatively, of at least 15° C. In some embodiments,conditions capable of forming the N²-phosphinyl formamidine metal saltcomplex can include a contact temperature ranging from 0° C. to 60° C.;alternatively, ranging from 5° C. to 50° C.; alternatively, ranging from10° C. to 45° C.; or alternatively, ranging from 15° C. to 40° C. In anembodiment, conditions capable of forming the N²-phosphinyl formamidinemetal salt complex can include a contact time of at least 15 minutes;alternatively, of at least 30 minutes; alternatively, of at least 45minutes; or alternatively, of at least 1 hour. In some embodiments,conditions capable of forming the N²-phosphinyl formamidine metal saltcomplex can include a contact time ranging from 15 minutes to 36 hours;alternatively, ranging from 30 minutes to 30 hours; alternatively,ranging from 45 minutes to 24 hours; or alternatively, ranging from 1hour to 18 hours.

In an embodiment, the metal salt and the N²-phosphinyl formamidinecompound can be contacted in a solvent. In some embodiments, the metalsalt and the N²-phosphinyl formamidine compound can be contacted in apolar solvent. In some embodiments, the solvent is the same as theneutral ligand, Q, within some embodiments of the N²-phosphinylformamidine metal salt complex. Solvents (general and specific) aregenerally disclosed herein and can be utilized, without limitation, tofurther describe the method of preparing the N²-phosphinyl formamidinemetal salt complex.

In an embodiment, the N²-phosphinyl formamidine metal salt complex canbe utilized without further isolation or purification. In someembodiments, the N²-phosphinyl formamidine metal salt complex can beisolated; alternatively, purified; or alternatively, isolated andpurified. In an embodiment, wherein the N²-phosphinyl formamidine metalsalt complex is prepared in a solvent, the method to prepare theN²-phosphinyl formamidine metal salt complex can include a step ofisolating the N²-phosphinyl formamidine metal salt complex byevaporating the solvent. In an embodiment wherein the N²-phosphinylformamidine metal salt complex is prepared in a solvent, the method toprepare the N²-phosphinyl formamidine metal salt complex can include thestep of isolating the N²-phosphinyl formamidine metal salt complex byfiltering the solution to remove particulate materials and/or byproductsof the reaction and evaporating the solvent. In embodiments, the methodto prepare the N²-phosphinyl formamidine metal salt complex can includea purification step wherein the N²-phosphinyl formamidine compound ispurified by dissolving the N²-phosphinyl formamidine metal salt complexin a solvent and filtering the solution to remove particulate materialsand/or byproducts of the reaction. The solvent utilized to purify theN²-phosphinyl formamidine metal salt complex can be the same as thesolvent utilized to form the N²-phosphinyl formamidine metal saltcomplex or it can be different than the solvent utilized to form theN²-phosphinyl formamidine metal salt complex. In some embodiments, themethod of preparing the N²-phosphinyl formamidine metal salt complex caninclude a purification step of isolating the N²-phosphinyl formamidinemetal salt complex by washing the N²-phosphinyl formamidine metal saltcomplex with a solvent. In other embodiments, the method of preparingthe N²-phosphinyl formamidine metal salt complex can include apurification step of recrystallizing the N²-phosphinyl formamidine metalsalt complex.

Generally, evaporation of the solvent can be performed using anysuitable method. In some embodiments, the solvent can be evaporated atambient temperature (15-35° C.—no applied external heat source). Inother embodiments, the solvent can be evaporated with gentle heating(e.g. at a temperature ranging from 25° C. to 50° C.). In furtherembodiments, the solvent can be evaporated at ambient temperature underreduced pressure. In yet other embodiments, the solvent can beevaporated with gentle heating under reduced pressure.

In an embodiment, the time between the isolation and/or purification ofthe N²-phosphinyl formamidine metal salt complex and the formation ofthe catalyst system can have an impact on aspects of the oligomerization(or polymerization) process. In some embodiments, increasing the timebetween the isolation and/or purification of the N²-phosphinylformamidine metal salt complex and the formation of the catalyst systemcan increase the catalytic activity and/or increase the productivity ofthe catalyst system. In other embodiments, increasing the time betweenthe isolation and/or purification of the N²-phosphinyl formamidine metalsalt complex and the formation of the catalyst system can increase thepercentage of polymer produced by the catalyst system. Without beinglimited by theory, it is believed that these effects result from thedisassociation of (or alternatively, evaporation of) neutral ligand, Q,from the N²-phosphinyl formamidine metal salt complex and/or from thecrystal lattice of the N²-phosphinyl formamidine metal salt complex.Herein “formation of the catalyst system” refers to the point at whichthe minimal number of catalyst system components are contacted toproduce a mixture capable of catalyzing an oligomerization process.

Controlling the time between the isolation and/or purification of theN²-phosphinyl formamidine metal salt complex and the formation of thecatalyst system can improve the oligomerization process. For instance,one can increase the activity and/or productivity of the catalyst systemby increasing the time between the isolation and/or purification of theN²-phosphinyl formamidine metal salt complex and formation of thecatalyst system. Increasing the activity and/or the productivity of thecatalyst system can provide increased oligomer product per unit ofcatalyst system.

However, it may not be possible to increase the time between theisolation and/or purification of the N²-phosphinyl formamidine metalsalt complex and formation of the catalyst system indiscriminately. Asnoted herein, increasing the time between the isolation and/orpurification of the N²-phosphinyl formamidine metal salt complex and theformation of the oligomerization catalyst system can increase thepercentage of polymer produced by the catalyst system. If the polymerproduction of the catalyst system utilizing the N²-phosphinylformamidine metal salt complex increases too much, polymer productioncan adversely impact the oligomerization process. For example, polymercould adhere to the oligomerization reactor walls or cooling apparatusand cause fouling which can necessitate a reactor shut down to removethe polymer. Consequently, there can be a need to balance increases incatalyst system activity and/or productivity against increased polymerproduction.

In an embodiment, some of the effects of increasing the time between theisolation and/or purification of the N²-phosphinyl formamidine metalsalt complex and the formation of the catalyst system can be reversed byadding neutral ligand to the N²-phosphinyl formamidine metal saltcomplex. The ability to reverse some of the effects of increasing thetime between the isolation and/or purification of the N²-phosphinylformamidine metal salt complex and the formation of the catalyst systemcan negate potentially negative effects. Non-limiting examples ofnegative effects of increasing the time between the isolation and/orpurification of the N²-phosphinyl formamidine metal salt complex and theformation of the catalyst system can include 1) prohibiting the abilityto use an N²-phosphinyl formamidine metal salt complex by increasing thetime between the isolation and/or purification of the N²-phosphinylformamidine metal salt complex and the formation of the catalyst systemto a point wherein the formed catalyst system produces an undesirablequantity of polymer and 2) reducing the need to minimize the timebetween preparing the N²-phosphinyl formamidine metal salt complex andthe preparation of the catalyst system utilizing the N²-phosphinylformamidine metal salt complex. It should also be noted that theincremental loss of the neutral ligand can impact the catalyst systemand its subsequent use in an oligomerization. Consequently, while addingneutral ligand can reverse the effect of neutral ligand loss from theN²-phosphinyl formamidine metal salt complex, process and/or steps canbe implemented that can limit the loss of neutral ligand loss from theN²-phosphinyl formamidine metal salt complex as a method to control theeffects associated with the neutral ligand loss from the N²-phosphinylformamidine metal salt complex. For example, the N²-phosphinylformamidine metal salt complex can be stored in a sealed container(among other methods know to those having ordinary skill in the art) tolimit loss of neutral ligand from the N²-phosphinyl formamidine metalsalt complex. In an embodiment, the amount of neutral ligand present inthe N²-phosphinyl formamidine metal salt complex can be determined usingany suitable methodology. In some aspects, the amount of neutral ligandin one or more N²-phosphinyl formamidine metal salt complexes can bedetermined and/or monitored and the information utilized to determinesuitable modifications to the N²-phosphinyl formamidine metal saltcomplex to produce a user and/or process desired catalytic activity.

However, without being limited by theory, it has also been discoveredthat too much neutral ligand associated with the N²-phosphinylformamidine metal salt complex can significantly reduce or eliminate thecatalyst system oligomer productivity. Consequently, in someembodiments, precautions to control the amount of neutral ligandprovided to the N²-phosphinyl formamidine metal salt complex can betaken. Generally, addition of the neutral ligand to the N²-phosphinylformamidine metal salt complex can be accomplished by any suitablemethod. For example, the N²-phosphinyl formamidine metal salt complexcan be recrystallized from a solution containing a neutral ligand or theN²-phosphinyl formamidine metal salt complex can be placed in a solventcontaining a neutral ligand. Excess neutral ligand can be removed fromthe N²-phosphinyl formamidine metal salt complex by allowing the solventto evaporate or by increasing the time between the treatment of theN²-phosphinyl formamidine metal salt complex with the neutral ligand andthe formation of the catalyst system.

In an aspect, the isolated and/or purified N²-phosphinyl formamidinemetal salt complex can be utilized in catalyst system. Consequently, inan aspect, any process of producing a catalyst system disclosed hereinor any oligomerization (or polymerization) process can further comprisea step of aging the N²-phosphinyl formamidine metal salt complex. Inanother aspect, any process of producing a catalyst system disclosedherein or any oligomerization (or polymerization) process can furthercomprise a step of treating the N²-phosphinyl formamidine metal saltcomplex with a neutral ligand; or alternatively, 1) treating theN²-phosphinyl formamidine metal salt complex with a neutral ligand and2) allowing the treated N²-phosphinyl formamidine metal salt complex toage. In another aspect, any process of producing a catalyst systemdisclosed herein or any oligomerization (or polymerization) process canfurther comprise a step of treating an aged N²-phosphinyl formamidinemetal salt complex with a neutral ligand; or alternatively, 1) treatingthe N²-phosphinyl formamidine metal salt complex with a neutral ligandand 2) allowing the treated N²-phosphinyl formamidine metal salt complexto age.

In an aspect, the activity of any catalyst system disclosed hereinutilized in any oligomerization (or polymerization) method describedherein can be controlled by aging the N²-phosphinyl formamidine metalsalt complex. In an aspect, the activity of any catalyst systemdisclosed herein utilized in any oligomerization (or polymerization)method described herein can be controlled by treating the N²-phosphinylformamidine metal salt complex with a neutral ligand; oralternatively, 1) treating the N²-phosphinyl formamidine metal saltcomplex with a neutral ligand and 2) allowing the treated N²-phosphinylformamidine metal salt complex to age. In an aspect, the activity of anycatalyst system disclosed herein utilized in any oligomerization (orpolymerization) method described herein can be controlled by treating anaged N²-phosphinyl formamidine metal salt complex with a neutral ligand;or alternatively, 1) treating the N²-phosphinyl formamidine metal saltcomplex with a neutral ligand and 2) allowing the treated N²-phosphinylformamidine metal salt complex to age.

The catalytic activity of any catalyst system described hereincomprising any N²-phosphinyl formamidine metal salt complex describedherein in an oligomerization process can be defined as the grams ofoligomer product (or liquid oligomer product, or any other definedportion of the oligomerization product) produced per gram of metal ofthe metal salt in the N²-phosphinyl formamidine metal salt complexutilized. In an embodiment, the catalyst system activity of any catalystsystem described herein comprising any N²-phosphinyl formamidine metalsalt complex described herein can be increased by utilizing an agedN²-phosphinyl formamidine metal salt complex. This activity increase canbe described as a percentage increase in the catalyst system activityand can be related to the activity of the catalyst system prepared usinga fresh N²-phosphinyl formamidine metal salt complex, a₀. Generally, afresh N²-phosphinyl formamidine metal salt complex is one which has beenutilized to prepare a catalyst system within 7 days of its isolationand/or purification. It should be noted, a fresh N²-phosphinylformamidine metal salt complex does not contain excess neutral ligandwhich can give an inactive catalyst system (i.e. a catalyst system thatproduces less than 500 grams oligomer per gram metal of metal salt inthe N²-phosphinyl formamidine metal salt complex). The activity of thecatalyst system based upon an aged N²-phosphinyl formamidine metal saltcomplex can be denoted a_(x).

In an embodiment, the N²-phosphinyl formamidine metal salt complex canbe aged for a maximum of 730 days; alternatively, 550 days;alternatively, 450 days; alternatively, 365 days; alternatively, 330days; alternatively, 300 days; alternatively, 270 days; alternatively,240 days; alternatively, 210 days; or alternatively, 180 days. In someembodiments, the N²-phosphinyl formamidine metal salt complex can beaged for a minimum of 1 day; alternatively, 3 days; alternatively, 7days; alternatively, 14 days; alternatively, 28 days. In otherembodiments, the N²-phosphinyl formamidine metal salt complex can beaged from any minimum aging time provided herein to any maximum agingtime provided herein. In a non-limiting embodiment, the N²-phosphinylformamidine metal salt complex can be aged can be aged from 1 day to 730days; alternatively, from 3 days to 550 days; alternatively, from 3 daysto 330 days; or alternatively, from 7 days to 180 days. Other agingtimes are readily apparent from the present disclosure.

In an embodiment, aging the N²-phosphinyl formamidine metal salt complex(for any time period described herein) can increase the activity of anycatalyst system described herein utilizing any N²-phosphinyl formamidinemetal salt complex described herein by a minimum of 10%; alternatively,by at least 20%; alternatively, by at least 30%; alternatively, by atleast 40%; or alternatively, by at least 50%. In other embodiments,aging the N²-phosphinyl formamidine metal salt complex (for any timeperiod described herein) can increase the activity of any catalystsystem described herein utilizing any N²-phosphinyl formamidine metalsalt complex described herein by a maximum of 1500%; alternatively,1000%; alternatively, 750%; alternatively, 600%; or alternatively, 500%In some embodiments, aging the N²-phosphinyl formamidine metal saltcomplex (for any time period described herein) can increase the activityof any catalyst system described herein utilizing any N²-phosphinylformamidine metal salt complex described herein from any minimum valuedescribed herein to any maximum value described herein. In anon-limiting example, aging the N²-phosphinyl formamidine metal saltcomplex (for any time period described herein) can increase the activityof any catalyst system described herein utilizing any N²-phosphinylformamidine metal salt complex described herein from 10% to 1500%;alternatively, from 20% to 1000%; alternatively, from 30% to 750%;alternatively, from 40% to 600%; or alternatively, from 50% to 500%.Other catalyst system activity ranges are readily apparent from thepresent disclosure.

In an embodiment, aging the N²-phosphinyl formamidine metal salt complex(for any time period described herein) for any catalyst system describedherein utilizing any N²-phosphinyl formamidine metal salt complexdescribed herein can provide a catalyst system which can produce anydefined percentage of polymer described herein. In an embodiment, agingthe N²-phosphinyl formamidine metal salt complex (for any time perioddescribed herein) for any catalyst system described herein utilizing anyN²-phosphinyl formamidine metal salt complex described herein canprovide a catalyst system which can produce less than 5 weight percentpolymer; alternatively, less than 2 weight % polymer; alternatively,less than 1.5 weight % polymer; alternatively, less than 1 weight %polymer; alternatively, less than 0.75 weight % polymer; alternatively,less than 0.5 weight % polymer; alternatively, less than 0.4 weight %polymer; alternatively, less than 0.3 weight % polymer; alternatively,less than 0.2 weight % polymer; or alternatively, equal to or less than0.1 weight % polymer. Generally, the basis for weight percent polymer isbased upon all products of the oligomerization (excluding unreactedmonomer, catalyst system components, solvent, and othernon-oligomerization products).

In some embodiments, any catalyst system described herein utilizing anaged N²-phosphinyl formamidine metal salt complex can have a combinationof any increased activity described herein and any amount of polymerdescribed herein. The catalyst system described herein utilizing an agedN²-phosphinyl formamidine metal salt complex can further be describedutilizing, individually or in any combination, any other catalyst systemfeature or oligomerization product feature described herein.

In an embodiment, a calibration curve can be produced depictingoligomerization catalytic activity and/or polymer production of anycatalyst system described herein comprising any N²-phosphinylformamidine metal salt complex described herein in response to aging theN²-phosphinyl formamidine metal salt complex. In some embodiments, acalibration curve (for catalyst activity and/or polymer production) canbe depicted as a function of the period of N²-phosphinyl formamidinemetal salt complex age in order to derive a predictive equation. Thecalibration curve or predictive equation relating catalyst systemactivity and/or polymer production in response to N²-phosphinylformamidine metal salt complex age can be utilized to adjust one or moreuser and/or process parameters based upon the interpolation orextrapolation the calibration curve and/or the predictive equation. Itis contemplated that in some aspects, the extent to which a_(x)increases with respect to a₀ can fall outside the instantly disclosedranges and can be larger than would be expected based on the presentlydisclosed values depending on conditions under which the N²-phosphinylformamidine metal salt complex is aged. For example, the N²-phosphinylformamidine metal salt complex can be subjected to aging for timeperiods that are 5 to 10 times longer than those presently recited orunder conditions of elevated temperature and/or reduced pressure. Theeffects of aging the N²-phosphinyl formamidine metal salt complex undersuch conditions can be subject to the herein mentioned analysis toprovide predictive information that can lead one to conditions underwhich aging the N²-phosphinyl formamidine metal salt complex canincrease catalyst system activity using an aged N²-phosphinylformamidine metal salt complexes outside of the recited numericalranges. It is contemplated that given the benefits of this disclosureand using routine experimentation one having ordinary skill in the artcan modify the methodologies disclosed herein to alter theoligomerization catalytic system activity using an aged N²-phosphinylformamidine metal salt complexes to a desired value or range. Suchmodifications fall within the scope of this disclosure.

In an embodiment, contacting of the N²-phosphinyl formamidine metal saltcomplex (aged or otherwise) with a neutral ligand can be carried outusing any suitable molar ratio of neutral ligand to N²-phosphinylformamidine metal salt. In an embodiment, the molar ratio of neutralligand to N²-phosphinyl formamidine metal salt complex can be at least0.2:1; alternatively, at least 0.3:1; alternatively, at least 0.4:1; oralternatively, at least 0.5:1. In an embodiment, the molar ratio ofneutral ligand to N²-phosphinyl formamidine metal salt complex can befrom 0.2:1 to 10,000:1; alternatively, 0.3:1 to 8,000:1; alternatively,from 0.4:1 to 6,000:1; or alternatively, from 0.5:1 to 5,000:1. In anembodiment, contact of the N²-phosphinyl formamidine metal salt complexcan occur in a solvent consisting essentially of the neutral ligand; oralternatively, in a solvent comprising, or consisting essentially of,the neutral ligand and a non-complexing solvent.

When the N²-phosphinyl formamidine metal salt complex is contacted witha solvent consisting essentially of the neutral ligand, the molar ratioof neutral ligand to N²-phosphinyl formamidine metal salt can be anymolar ratio of neutral ligand to N²-phosphinyl formamidine metal saltcomplex disclosed herein. In other embodiments wherein the N²-phosphinylformamidine metal salt complex is contacted with a solvent consistingessentially of the neutral ligand, the molar ratio of neutral ligand toN²-phosphinyl formamidine metal salt complex can be at least 5:1;alternatively, at least 7.5:1; alternatively, at least 10:1;alternatively, at least 10:1; alternatively, at least 15:1;alternatively, 5:1; alternatively, range from 7.5:1 to 10,000:1;alternatively, range from 10:1 to 8,000:1; alternatively, range from10:1 to 6,000:1; or alternatively, range from 15:1 to 5,000:1.

When the N²-phosphinyl formamidine metal salt complex is contacted witha solvent comprising, or consisting essentially of, the neutral ligandand a non-complexing solvent, the molar ratio of neutral ligand toN²-phosphinyl formamidine metal salt can be any molar ratio of neutralligand to N²-phosphinyl formamidine metal salt disclosed herein. Inother embodiments wherein the N²-phosphinyl formamidine metal saltcomplex is contacted with a solvent comprising, or consistingessentially of, the neutral ligand and a non-complexing solvent, themaximum molar ratio of neutral ligand to N²-phosphinyl formamidine metalsalt can be 500:1; alternatively, 300:1; alternatively, 200:1;alternatively, 100:1; alternatively, from 0.2:1 to 500:1; alternatively,from 0.3:1 to 300:1; alternatively, from 0.4:1 to 200:1; oralternatively, 0.5:1 to 100:1. In some embodiments, wherein theN²-phosphinyl formamidine metal salt complex is contacted with a solventcomprising, or consisting essentially of, the neutral ligand and anon-complexing solvent, the volumetric ratio of neutral ligand tonon-complexing solvent can range from 1:1 to 10,000:1; alternatively,range from 5:1 to 8,000:1; alternatively, range from 7.5:1 to 6,000:1;or alternatively, range from 10:1 to 5,000:1.

In an embodiment, the neutral ligand can be any neutral ligand disclosedherein. In some embodiments, the neutral ligand utilized to treat theN²-phosphinyl formamidine metal salt complex can be the same or the sameas the neutral ligand of the N²-phosphinyl formamidine metal saltcomplex; or alternatively, the neutral ligand utilized to treat theN²-phosphinyl formamidine metal salt complex can be different from theneutral ligand of the N²-phosphinyl formamidine metal salt complex. Inan embodiment, the non-complexing solvent utilized in an embodimentcomprising, or consisting essentially of, a neutral ligand and anon-complexing solvent can be a hydrocarbon or a halogenatedhydrocarbon; alternatively, a hydrocarbon or a halogenated hydrocarbon.Hydrocarbon and halogenated hydrocarbon solvents (general and specific)are disclosed herein and can be utilized, without limitation, to furtherdescribe any aspect and/or embodiment utilizing a solvent comprising, orconsisting essentially of, a neutral ligand and a non-complexingsolvent.

In an embodiment, the N²-phosphinyl formamidine metal salt complex canbe aged (whether or not it has been treated with a neutral ligand)utilizing any suitable methodology. In some embodiments, theN²-phosphinyl formamidine metal salt complex can be aged (whether or notit has been treated with a neutral ligand) at ambient temperature(15-35° C.—no applied external heat source); or alternatively, atambient temperature under an inert atmosphere. In other embodiments, theN²-phosphinyl formamidine metal salt complex can be aged (whether or notit has been treated with a neutral ligand) with gentle heating (e.g., ata temperature ranging from 25° C. to 50° C.); alternatively, underreduced pressure; alternatively ambient temperature under reducedpressure; or alternatively, with gentle heating under reduced pressure.

In an embodiment, the aged N²-phosphinyl formamidine metal salt complex,the neutral ligand treated N²-phosphinyl formamidine metal salt complex,or the neutral ligand treated and aged N²-phosphinyl formamidine metalsalt complex can be utilized in a catalyst system, utilized in a processto prepare a catalyst system, and/or a method to oligomerize (orpolymerize) an olefin. Generally, the steps of aging the N²-phosphinylformamidine metal salt complex, the steps of treating the N²-phosphinylformamidine metal salt complex with a neutral ligand, and/or treatingthe N²-phosphinyl formamidine metal salt complex with a neutral ligandand aging the neutral ligand treated the N²-phosphinyl formamidine metalsalt complex can be utilized, without limitation, to further describethe catalyst system, the method of preparing the catalyst system, and/orthe method to oligomerize (or polymerize) an olefin.

In an aspect, the step(s) for preparing the formamidine compound can beincorporated into the preparation of the N²-phosphinyl formamidine metalsalt complex. When the steps are combined, appropriate step identifiers(e.g. 1), 2), etc. . . . , a), b), etc. . . . , or i), ii), etc. . . . )and compound/solvent identifiers (e.g. first, second, etc . . . ) can beadded to indicate individual and/or different steps/compounds/solventsutilized within the preparation of the N²-phosphinyl formamidine metalsalt complex without detracting from the general disclosure.

Methods of Oligomerizing or Polymerizing Olefins.

In an embodiment, the process can comprise: a) contacting an olefin anda catalyst system; and b) forming an oligomer product. In someembodiments, the process can comprise, a) contacting an olefin,hydrogen, and a catalyst system; and b) forming an oligomer product. Inan embodiment, the process can comprise: a) contacting an olefin and acatalyst system; and b) forming a polymer product. In some embodiments,the process can comprise a) contacting an olefin, hydrogen, and acatalyst system and b) forming a polymer product. The catalyst system,olefin, and features of the oligomer or polymer product areindependently described herein and can be utilized, without limitationto further describe the process. In an embodiment, the catalyst systemcan be prepared in a first solvent. In an embodiment, the olefin,catalyst system, and optionally hydrogen, can be contacted in a secondsolvent. Generally, a solvent in which the catalyst system can beprepared and the solvent in which the olefin and catalyst system can becontacted can be the same; or alternatively, can be different.

In an embodiment, the process can comprise: a) forming a catalyst systemmixture comprising an N²-phosphinyl formamidine metal salt complex and ametal alkyl; b) contacting the catalyst system mixture with an olefin;and c) forming an oligomer product. In an embodiment, the process cancomprise: a) forming a catalyst system mixture comprising anN²-phosphinyl formamidine metal salt complex and a metal alkyl; b)contacting the catalyst system mixture with an olefin; and c) forming anoligomer product. In some embodiments, the step of contacting thecatalyst system mixture with the olefin can be a step of contacting thecatalyst system mixture with an olefin and hydrogen. In someembodiments, the catalyst system mixture can further comprise a solvent(e.g. a first solvent). In some embodiments, the catalyst system mixtureand olefin can be contacted in a solvent (e.g. a second solvent when thecatalyst system is prepared in a solvent). In an embodiment, the processcan comprise: a) forming a catalyst system mixture comprising, orconsisting essentially of, an N²-phosphinyl formamidine metal saltcomplex, a metal alkyl, and a first solvent; b) contacting the catalystsystem mixture with an olefin and a second solvent; and c) forming anoligomer product. In an embodiment, the process can comprise: a) forminga catalyst system mixture comprising, or consisting essentially of, anN²-phosphinyl formamidine metal salt complex, a metal alkyl, and a firstsolvent; b) contacting the catalyst system mixture with an olefin and asecond solvent; and c) forming a polymer product. In some embodiments,the step of contacting the catalyst system mixture with the olefin andthe second solvent can be a step of contacting the catalyst systemmixture with an olefin, a second solvent, and hydrogen. TheN²-phosphinyl formamidine metal salt complex, metal alkyl, olefin,solvents, and features of the oligomer or polymer product areindependently described herein (among other catalyst system andoligomerization or polymerization features) and can be utilized, withoutlimitation to further describe the oligomerization or polymerizationprocess. In some embodiments, the first and second solvent can be thesame; or alternatively, the first and second solvent can be different.In some embodiments, the metal alkyl can comprise, or consistessentially of, an aluminoxane. Ratios for the metal of theN²-phosphinyl formamidine metal salt complex to the metal of the metalalkyl are independently provided herein (among other catalyst system andoligomerization or polymerization features) and can be utilized withoutlimitation to further describe the oligomerization or polymerizationprocess.

In an embodiment, the process can comprise: a) forming a catalyst systemmixture comprising an N²-phosphinyl formamidine compound, a metal salt,and a metal alkyl; b) contacting the catalyst system mixture with anolefin; and c) forming an oligomer product. In an embodiment, theprocess can comprise: a) forming a catalyst system mixture comprising anN²-phosphinyl formamidine compound, a metal salt, and a metal alkyl; b)contacting the catalyst system mixture with an olefin; and c) forming apolymer product. In some embodiments, the step of contacting thecatalyst system mixture with the olefin can be a step of contacting thecatalyst system mixture with an olefin and hydrogen. In someembodiments, the catalyst system mixture can further comprise a solvent(e.g. a first solvent). In some embodiments, the catalyst system mixtureand olefin can be contacted in a solvent (e.g. a second solvent when thecatalyst system is prepared in a solvent). In an embodiment, the processcan comprise: a) forming a catalyst system mixture comprising, orconsisting essentially of, an N²-phosphinyl formamidine compound, ametal salt, a metal alkyl, and a first solvent; b) contacting thecatalyst system mixture with an olefin and a second solvent; and c)forming an oligomer product. In an embodiment, the process can comprise:a) forming a catalyst system mixture comprising, or consistingessentially of an N²-phosphinyl formamidine compound, a metal salt, ametal alkyl, and a first solvent; b) contacting the catalyst systemmixture with an olefin and a second solvent; and c) forming a polymerproduct. In some embodiments, the step of contacting the catalystmixture with the olefin and the second solvent can be a step ofcontacting the catalyst system mixture with an olefin, a second solvent,and hydrogen. In some embodiments, the first and second solvent can bethe same; or alternatively, the first and second can be different. TheN²-phosphinyl formamidine compound, metal salt, metal alkyl, olefin,solvents, and features of the oligomer or polymer product areindependently described herein (among other catalyst system andoligomerization or polymerization features) and can be utilized, withoutlimitation to further describe the oligomerization or polymerizationprocess. In some embodiments, the first and second solvent can be thesame; or alternatively, the first and second solvent can be different.In some embodiments, the metal alkyl can comprise, or consistessentially of, an aluminoxane. The N²-phosphinyl formamidine compound,metal salt, metal alkyl, olefin, solvents, and features of the oligomeror polymer product are independently described herein (among othercatalyst system and oligomerization or polymerization features) and canbe utilized, without limitation to further describe the process. Ratiosfor the N²-phosphinyl formamidine compound to metal salt and ratios forthe metal of the metal alkyl to metal of the metal salt areindependently provided herein (among other catalyst system andoligomerization or polymerization features) and can be utilized withoutlimitation to further describe the process.

In an embodiment, a solvent utilized with the catalyst system, a mixturecomprising an N²-phosphinyl formamidine metal salt complex, a mixturecomprising an N²-phosphinyl formamidine metal salt complex and a metalalkyl, a composition comprising an N²-phosphinyl formamidine compoundand a metal salt, or a composition comprising an N²-phosphinylformamidine compound, a metal salt, and a metal alkyl can be ahydrocarbon solvent, a halogenated hydrocarbon solvent, or anycombination thereof; alternatively, a hydrocarbon solvent; oralternatively, a halogenated hydrocarbon solvent. In some embodiments, asolvent utilized with a mixture comprising an N²-phosphinyl formamidinemetal salt complex, a mixture comprising an N²-phosphinyl formamidinemetal salt complex and a metal alkyl, a composition comprising anN²-phosphinyl formamidine compound and a metal salt, or a compositioncomprising an N²-phosphinyl formamidine compound, a metal salt, and ametal alkyl can be an aliphatic hydrocarbon solvent, a halogenatedaliphatic hydrocarbon solvent, an aromatic hydrocarbon solvent, ahalogenated aromatic solvent, or any combination thereof; alternatively,an aliphatic hydrocarbon solvent, a halogenated aliphatic hydrocarbonsolvent, or any combination thereof; alternatively, an aromatichydrocarbon solvent, a halogenated aromatic solvent, or any combinationthereof; alternatively, an aliphatic hydrocarbon solvent; alternatively,a halogenated aliphatic hydrocarbon solvent; alternatively, an aromatichydrocarbon solvent; or alternatively, a halogenated aromatic solvent.General and specific hydrocarbon solvents, halogenated hydrocarbonsolvents, aliphatic hydrocarbon solvents, halogenated aliphatichydrocarbon solvents, aromatic hydrocarbon solvents, and halogenatedaromatic solvents are described herein and can be utilized withoutlimitation to further describe the process(es) described herein.

In an embodiment, a solvent utilized in any mixture including the olefinor utilized to form the oligomer product or polymer product can behydrocarbon solvent, a halogenated hydrocarbon solvent, or anycombination thereof; alternatively, a hydrocarbon solvent; oralternatively, a halogenated hydrocarbon solvent. In some embodiments, asolvent utilized in any mixture including the olefin or utilized to formthe oligomer product or polymer product can be an aliphatic hydrocarbonsolvent, a halogenated aliphatic hydrocarbon solvent, an aromatichydrocarbon solvent, a halogenated aromatic solvent, or any combinationthereof; alternatively, an aliphatic hydrocarbon solvent, a halogenatedaliphatic hydrocarbon solvent, or any combination thereof;alternatively, an aromatic hydrocarbon solvent, a halogenated aromaticsolvent, or any combination thereof; alternatively, an aliphatichydrocarbon solvent; alternatively, a halogenated aliphatic hydrocarbonsolvent; alternatively, an aromatic hydrocarbon solvent; oralternatively, a halogenated aromatic solvent. General and specifichydrocarbon solvents, halogenated hydrocarbon solvents, aliphatichydrocarbon solvents, halogenated aliphatic hydrocarbon solvents,aromatic hydrocarbon solvents, and halogenated aromatic solvents aredescribed herein and can be utilized without limitation to furtherdescribe the processes disclosed herein.

In some embodiments, the solvent utilized with the catalyst system, amixture comprising an N²-phosphinyl formamidine metal salt complex, amixture comprising an N²-phosphinyl formamidine metal salt complex and ametal alkyl, a composition comprising an N²-phosphinyl formamidinecompound and a metal salt, or a composition comprising an N²-phosphinylformamidine compound, a metal salt, and a metal alkyl and the solventutilized in any mixture including the olefin or utilized to form theoligomer product or polymer product can be the same; or alternativelycan be different. In an embodiment, the solvent utilized with thecatalyst system, a mixture comprising an N²-phosphinyl formamidine metalsalt complex, a mixture comprising an N²-phosphinyl formamidine metalsalt complex and a metal alkyl, a composition comprising anN²-phosphinyl formamidine compound and a metal salt, or a compositioncomprising an N²-phosphinyl formamidine compound, a metal salt, and ametal alkyl and the solvent utilized in any mixture including the olefinor utilized to form the oligomer product or polymer product has aboiling point which allows for its easy separation (e.g. bydistillation) from the oligomer product or polymer product.

Generally, the olefin which can be oligomerized or polymerized cancomprise, or consist essentially of, a C₂ to C₃₀ olefin; alternatively,a C₂ to C₁₆ olefin; or alternatively, a C₂ to C₁₀ olefin. In anembodiment, the olefin can be an alpha olefin; alternatively, a linearalpha olefin; or alternatively a normal alpha olefin. In an embodiment,the olefin can comprise, or consist essentially of, ethylene, propylene,or a combination thereof; alternatively ethylene; or alternatively,propylene. When the olefin consists essentially of ethylene, theoligomerization process can be an ethylene oligomerization process or anethylene polymerization process.

In an aspect, the process can be a trimerization process; alternatively,a tetramerization process; or alternatively, a trimerization andtetramerization process. When the olefin is ethylene, the process can bean ethylene trimerization process; alternatively, an ethylenetetramerization process; or alternatively, an ethylene trimerization andtetramerization process. When the process is an ethylene trimerizationprocess, the oligomer product can comprise hexene; or alternatively,1-hexene. When the process is an ethylene tetramerization process, theoligomer product can comprise octene; or alternatively, 1-octene. Whenthe process is an ethylene trimerization and tetramerization process,the oligomer product can comprise hexene and octene; or alternatively,1-hexene and 1-octene.

Unless otherwise specified, the terms contacted, combined, and “in thepresence of” refer to any addition sequence, order, or concentration forcontacting or combining two or more components of the oligomerizationprocess. Combining or contacting of oligomerization components,according to the various methods described herein can occur in one ormore contact zones under suitable contact conditions such astemperature, pressure, contact time, flow rates, etc. . . . . Thecontact zone can be disposed in a vessel (e.g. a storage tank, tote,container, mixing vessel, reactor, etc.), a length of pipe (e.g. a tee,inlet, injection port, or header for combining component feed lines intoa common line), or any other suitable apparatus for bringing thecomponents into contact. The processes can be carried out in a batch orcontinuous process as is suitable for a given embodiment.

In an embodiment, the process can be a continuous process carried out inone or more reactors. In some embodiments, the continuous reactor cancomprise a circular recycle reactor, a tubular reactor, a continuousstirred tank reactor (CSTR), or combinations thereof. In otherembodiments, the continuous reactor can be a recycle reactor;alternatively, a tubular reactor; or alternatively, a continuous stirredtank reactor (CSTR). In other embodiments, the continuous reactor can beemployed in the form of different types of continuous reactors incombination, and in various arrangements.

In an embodiment, the oligomer product or polymer product can be formedunder suitable reaction conditions such as reaction temperatures,reaction pressure, and/or reaction times. Reaction temperatures,reaction pressure, and/or reaction times can be impacted by a number offactors such as the metal complex stability, metal complex activity,cocatalyst identity, cocatalyst activity, desired product distribution,and/or desired product purity among other factors.

Generally, the processes can be performed using any N²-phosphinylformamidine compound, metal salt, or N²-phosphinyl formamidine metalsalt complex concentration that forms the desired oligomer product orpolymer product. In an embodiment, the concentration of theN²-phosphinyl formamidine compound, metal salt, or N²-phosphinylformamidine metal salt complex can be at least 1×10⁻⁶ equivalents/liter;alternatively, at least 1×10⁻⁵ equivalents/liter; or alternatively, atleast 5×10⁻⁴ equivalents/liter. In other embodiments, the concentrationof the diphosphino aminyl complexed metal compound can range from 1×10⁻⁶equivalents/liter to 1 equivalents/liter; alternatively, range from1×10⁻⁵ equivalents/liter to 5×10⁻¹ equivalents/liter; or alternatively,range from 5×10⁻⁴ equivalents/liter to 1×10⁻¹ equivalents/liter.

Generally, the reaction pressure can be any pressure that facilitatesthe oligomerization or polymerization of the olefin. In an embodiment,the reaction pressure of the process can be any reaction pressurerequired to produce the desired oligomer product or polymer product. Insome embodiments, the pressure can be greater than or equal to 0 psig (0KPa); alternatively, greater than or equal to 50 psig (344 KPa);alternatively, greater than or equal to 100 psig (689 KPa); oralternatively, greater than or equal to 150 psig (1.0 MPa). In otherembodiments, the pressure can range from 0 psig (0 KPa) to 5,000 psig(34.5 MPa); alternatively, 50 psig (344 KPa) to 4,000 psig (27.6 MPa);alternatively, 100 psig (689 KPa) to 3,000 psig (20.9 MPa); oralternatively, 150 psig (1.0 MPa) to 2,000 psig (13.8 MPa). Inembodiments wherein the monomer is a gas (e.g. ethylene), the pressurecan be carried out under a monomer gas pressure. When the monomer isethylene, the reaction pressure can be the monomer ethylene pressure. Insome embodiments, the ethylene pressure can be greater than or equal to0 psig (0 KPa); alternatively, greater than or equal to 50 psig (344KPa); alternatively, greater than or equal to 100 psig (689 KPa); oralternatively, greater than or equal to 150 psig (1.0 MPa). In otherembodiments, the ethylene pressure can range from 0 psig (0 KPa) to5,000 psig (34.5 MPa); alternatively, 50 psig (344 KPa) to 4,000 psig(27.6 MPa); alternatively, 100 psig (689 KPa) to 3,000 psig (20.9 MPa);or alternatively, 150 psig (1.0 MPa) to 2,000 psig (13.8 MPa). In somecases when ethylene is the monomer, inert gases can form a portion ofthe total reaction pressure. In the cases where inert gases form aportion of the reaction pressure, the previously stated ethylenepressures can be the applicable ethylene partial pressures of thepolymerization or oligomerization. In the situation where the monomerprovides all or a portion of the oligomerization or polymerizationpressure, the reaction system pressure can decrease as the gaseousmonomer is consumed. In this situation, additional gaseous monomerand/or inert gas can be added to maintain a desired pressure or monomerpartial pressure. In some embodiments, additional gaseous monomer can beadded at a set rate (e.g. for a continuous flow reactor), or atdifferent rates (e.g. to maintain a set system pressure in a batchreactor). In other embodiments, the pressure can be allowed to decreasewithout adding any additional gaseous monomer and/or inert gas.

In embodiments wherein hydrogen is utilized, hydrogen can be added inany amount that produces the desired effect. In some embodiments, thehydrogen partial pressure can be greater than or equal to 1 psig (kPa);alternatively, greater than or equal to 5 psig (34 kPa); alternatively,greater than or equal to 10 psig (69 kPa); or alternatively, greaterthan or equal to 15 psig (100 kPa). In other embodiments, the hydrogenpartial pressure can range from 1 psig (6.9 kPa) to 500 psig (3.5 MPa);alternatively, 5 psig (34 kPa) to 400 psig (2.8 MPa); alternatively, 10psig (69 kPa) to 300 psig (2.1 MPa); or alternatively, 15 psig (100 kPa)to 200 psig (1.4 MPa).

In an embodiment, a condition to form an oligomer product or polymerproduct can include an oligomerization temperature or polymerizationtemperature. Generally, the oligomerization temperature orpolymerization temperature can be any temperature which forms thedesired oligomer product or polymer product. In an embodiment, thetemperature can be at least 0° C.; alternatively, at least 10° C.;alternatively, at least 20° C.; or alternatively, at least 30° C. Insome embodiments, the temperature can range from 0° C. to 200° C.;alternatively, range from 10° C. to 160° C.; alternatively, ranges from20° C. to 140° C.; or alternatively, ranges from 30° C. to 120° C.

In an embodiment, a condition to form an oligomer product or polymerproduct can include an oligomerization time or polymerization time.Generally, the time can be any time that produces the desired quantityof oligomer product or polymer product; or alternatively, provides adesired catalyst system productivity; or alternatively, provides adesired conversion of monomer. In some embodiments, the time can rangefrom 1 minute to 5 hours; alternatively, ranges from 5 minutes to 2.5hours; alternatively, ranges from 10 minutes to 2 hours; oralternatively, ranges from 15 minutes to 1.5 hours. In an embodiment,the oligomerization or polymerization can have a single pass olefinconversion of ethylene of at least 30 wt. % percent; alternatively, atleast 35 wt. % percent; alternatively, at least 40 wt. % percent; oralternatively, at least 45 wt. % percent. When the olefin is ethylene,the olefin conversion is ethylene conversion.

In an aspect, the catalyst system productivity for the oligomerizationprocess can be any catalyst system productivity which provides adesirable oligomer product. In an embodiment, the minimum catalystsystem productivity can be 1×10³ grams (g) oligomer product/mmoltransition metal of the N²-phosphinyl formamidine metal salt complex;alternatively, 5×10³ g oligomer product/mmol N²-phosphinyl formamidinemetal salt complex; alternatively, 1×10⁴ g oligomer product/mmolN²-phosphinyl formamidine metal salt complex; alternatively, 5×10⁴ goligomer product/mmol N²-phosphinyl formamidine metal salt complex;alternatively, 1×10⁵ g oligomer product/mmol N²-phosphinyl formamidinemetal salt complex; or alternatively, 5×10³ g oligomer product/mmolN²-phosphinyl formamidine metal salt complex. In an embodiment, themaximum catalyst system productivity can be 1×10⁸ g oligomerproduct/N²-phosphinyl formamidine metal salt complex; alternatively,5×10⁷ g oligomer product/mmol N²-phosphinyl formamidine metal saltcomplex; alternatively, 1×10⁷ g oligomer product/mmol N²-phosphinylformamidine metal salt complex; alternatively, 5×10⁶ g oligomerproduct/mmol N²-phosphinyl formamidine metal salt complex; oralternatively, 1×10⁶ g oligomer product/N²-phosphinyl formamidine metalsalt complex. In some embodiments, the catalyst system productivity canrange from any minimum catalyst system productivity described herein toany maximum catalyst system productivity described herein. For example,in some non-limiting embodiments, the catalyst system productivity canrange from 1×10³ to 1×10⁸ g oligomer product/N²-phosphinyl formamidinemetal salt complex; alternatively, 5×10³ to 5×10⁷ g oligomerproduct/N²-phosphinyl formamidine metal salt complex; alternatively,5×10⁴ to 5×10⁷ g oligomer product/mmol N²-phosphinyl formamidine metalsalt complex; or alternatively, 1×10⁵ to 1×10⁷ g oligomer product/mmolN²-phosphinyl formamidine metal salt complex. Other catalyst systemproductivities are readily apparent from the present disclosure. When aspecific transition metal of the transition metal complex is utilized,the catalyst system productivity can be provided utilizing the specifictransition metal; for example when a chromium N²-phosphinyl formamidinemetal salt complex is utilized, the catalyst system productivity can beprovided in units of g oligomer product/mmol Cr.

In an aspect, the catalyst system activity for the oligomerizationprocess can be any catalyst system activity which provides a desirableamount of oligomer product under some user and/or process desiredcondition. Catalyst activity is defined as grams of a product producedper gram of metal of the metal compound (or metal complex) utilized inthe catalyst system over the first 30 minutes of an oligomerization orpolymerization reaction beginning from the time when the completecatalyst system is contacted with the olefin. Catalyst system activitycan be stated in terms of various products of an oligomerization orpolymerization. For example, in an ethylene oligomerization processutilizing a catalyst system comprising an iron complex as the metalcomplex, the catalyst system activities which can be utilized include (gethylene oligomer)/(g Fe), and (total oligomer product)/(g Fe), amongother activities.

In an embodiment, the process can produce an oligomer product comprisinga trimer, a tetramer, or mixtures thereof. In some embodiments, when theolefin is ethylene the process can be an ethylene oligomerizationprocess. In some embodiments, the process can produce an alpha olefinhaving at least four carbon atoms. In an embodiment, the ethyleneoligomerization process can produce an oligomer product comprising anethylene trimer (e.g. hexene, or alternatively, 1-hexene), an ethylenetetramer (e.g. octene, or alternatively, 1-octene), or a combinationthereof; alternatively, hexene; alternatively, octene; alternativelyhexene and octene. In other embodiments, the ethylene oligomerizationprocess can produce an oligomer product comprising 1-hexene, 1-octene,or a combination thereof; alternatively, 1-hexene; alternatively,1-octene; alternatively 1-hexene and 1-octene. In an embodiment, whenthe olefin is ethylene and the process can produce an alpha olefin (e.g.1-hexene, 1-octene, or a combination thereof), the process can be analpha olefin production process.

In an embodiment where the monomer comprises, consists essentially of,or consists of ethylene, the process can produce an oligomer productcomprising a liquid product comprising at least 60 wt. % C₆ and C₈olefins. In some embodiments where the monomer comprises, consistsessentially of, or consists of ethylene, the oligomer product cancomprise a liquid product comprising at least 70 wt. % C₆ and C₈olefins; alternatively, at least 75 wt. % C₆ and C₈ olefins;alternatively, at least 80 wt. % C₆ and C₈ olefins; alternatively, atleast 85 wt. % C₆ and C₈ olefins; or alternatively, at least 90 wt. % C₆and C₈ olefins. In other embodiments where the monomer comprises,consists essentially of, or consists of ethylene, the process canproduce an oligomer product comprising a liquid product having from 60to 99.9 wt. % of C₆ and C₈ olefins; alternatively, from 70 to 99.8 wt. %C₆ and C₈ olefins; alternatively, from 75 to 99.7 wt. % C₆ and C₃olefins; or alternatively, from 80 to 99.6 wt. % C₆ and C₃ olefins.Throughout this application, a liquid product refers to the oligomerproduct having from 4 to 18 carbon atoms.

In an embodiment where the monomer comprises, consists essentially of,or consists of ethylene, the process can produce an oligomer productcomprising a liquid product comprising at least 60 wt. % C₆ olefins. Insome embodiments where the monomer comprises, consists essentially of,or consists of ethylene, the process can produce an oligomer productcomprising a liquid product comprising at least 70 wt. % C₆ olefins;alternatively, at least 75 wt. % C₆ olefins; alternatively, at least 80wt. % C₆ olefins; alternatively, at least 85 wt. % C₆ olefins; oralternatively, at least 90 wt. % C₆ olefins. In other embodiments wherethe monomer comprises, consists essentially of, or consists of ethylene,the process can produce an oligomer product comprising a liquid producthaving from 60 to 99.9 wt. % of C₆ olefins; alternatively, from 70 to99.8 wt. % C₆ olefins; alternatively, from 75 to 99.7 wt. % C₆ olefins;or alternatively, from 80 to 99.6 wt. % C₆ olefins; or alternatively, 85to 99.6 wt. % C₆ olefins.

In an embodiment, the C₆ olefin product produced by the ethyleneoligomerization process can comprise at least 85 wt. % 1-hexene. In someembodiments, the C₆ olefin product produced by the ethyleneoligomerization process can comprise at least 87.5 wt. % 1-hexene;alternatively, at least 90 wt. % 1-hexene; alternatively, at least 92.5wt. % 1-hexene; alternatively, at least 95 wt. % 1-hexene;alternatively, at least 97 wt. % 1-hexene; or alternatively at least 98wt. % 1-hexene. In other embodiments, the C₆ olefin product produced bythe ethylene oligomerization process can comprise from 85 to 99.9 wt. %1-hexene; alternatively, from 87.5 to 99.9 wt. % 1-hexene;alternatively, from 90 to 99.9 wt. % 1-hexene; alternatively, from 92.5to 99.9 wt. % 1-hexene; alternatively, from 95 to 99.9 wt. % 1-hexene;alternatively, from 97 to 99.9 wt. % 1-hexene; or alternatively, from 98to 99.9 wt. % 1-hexene.

In an embodiment, the C₈ olefin product produced by the ethyleneoligomerization process can comprise at least 85 wt. % 1-octene. In someembodiments, the C₈ olefin product produced by the ethyleneoligomerization process can comprise at least 87.5 wt. % 1-octene;alternatively, at least 90 wt. % 1-octene; alternatively, at least 92.5wt. % 1-octene; alternatively, at least 95 wt. % 1-octene;alternatively, at least 97 wt. % 1-octene; or alternatively at least 98wt. % 1-octene. In other embodiments, the C₈ olefin product produced bythe ethylene oligomerization process can comprise from 85 to 99.9 wt. %1-octene; alternatively, from 87.5 to 99.9 wt. % 1-octene;alternatively, from 90 to 99.9 wt. % 1-octene; alternatively, from 92.5to 99.9 wt. % 1-octene; alternatively, from 95 to 99.9 wt. % 1-octene;alternatively, from 97 to 99.9 wt. % 1-octene; or alternatively, from 98to 99.9 wt. % 1-octene.

In some aspects and/or embodiments, aging the catalyst system (orcatalyst system mixture) before contacting the catalyst system (orcatalyst system mixture) with the olefin to be oligomerized and/orpolymerized can improve aspects of the oligomerization and/orpolymerization processes; or alternatively, aging the catalyst system(or a catalyst system mixture) in the substantial absence of an olefincan improve aspects of the oligomerization and/or polymerizationprocesses. In some embodiments, aging the catalyst system can increasethe productivity of the catalyst system. In other embodiments, aging thecatalyst system can decrease the amount of polymer produced in anoligomerization process. In some oligomerization process aspects and/orembodiments, aging the catalyst system can increase the productivity ofthe catalyst system; alternatively, can decrease the amount of polymerproduced in an oligomerization process; or alternatively, can increasethe productivity of the catalyst system and decrease the amount ofpolymer produced in the oligomerization. In regards to aging thecatalyst system (or catalyst system mixture) in the substantial absenceof an olefin, this can be taken to mean that the catalyst system (orcatalyst system mixture) can contain less than 1,000 ppm olefin, byweight. In some embodiments, the catalyst system (or catalyst systemmixture) can contain less than 500 ppm, by weight, olefin;alternatively, 250 ppm, by weight, olefin; alternatively, 100 ppm, byweight, olefin; alternatively, 75 ppm, by weight, olefin; alternatively,50 ppm, by weight, olefin; alternatively, 25 ppm, by weight, olefin;alternatively, 15 ppm, by weight, olefin; alternatively, 10 ppm, byweight, olefin; alternatively, 5 ppm, by weight, olefin; alternatively,2.5 ppm, by weight, olefin; or alternatively, 1 ppm, by weight, olefin.

The catalyst system aging impacts can be utilized to provide positivebenefits to an oligomerization and/or polymerization process. Forexample, increasing the activity and/or the productivity of the catalystsystem can provide increased oligomer product per unit of catalystsystem among other benefits. Additionally, in an oligomerizationprocess, the decrease in polymer produced in an oligomerization processupon aging the catalyst system can reduce the amount of polymer whichcould adhere to the oligomerization reactor walls or cooling apparatus.The reduction in polymer produced in the oligomerization process canreduce the need to shut down a reactor to remove the polymer which cancause fouling.

In any aspect and/or embodiment, a mixture comprising the N²-phosphinylformamidine compound, the metal salt, and the metal alkyl can be allowedto age for a period of time prior to contacting the mixture with theolefin to be oligomerized or polymerized (or a mixture comprising theolefin to be oligomerized or polymerized); or alternatively, a catalystsystem comprising the N²-phosphinyl formamidine compound, the metalsalt, and the metal alkyl can be allowed to age for a period of time inthe substantial absence of (or in the absence of) the olefin to beoligomerized or polymerized (or a mixture comprising the olefin to beoligomerized or polymerized). In some embodiments, a mixture (orcatalyst system) comprising an N²-phosphinyl formamidine compound, ametal salt, and a metal alkyl can further comprise a solvent.

In any aspect and/or embodiment, a mixture comprising the N²-phosphinylformamidine metal salt complex and the metal alkyl can be allowed to agefor a period of time prior to contacting the mixture with the olefin tobe oligomerized or polymerized (or a mixture comprising the olefin to beoligomerized or polymerized); or alternatively, a catalyst systemcomprising the N²-phosphinyl formamidine metal salt complex and themetal alkyl can be allowed to age for a period of time in thesubstantial absence of (or in the absence of) the olefin to beoligomerized or polymerized (or a mixture comprising the olefin to beoligomerized or polymerized). In some embodiments, a mixture (orcatalyst system) comprising an N²-phosphinyl formamidine metal saltcomplex and a metal alkyl can further comprise a solvent.

In a non-limiting embodiment, the oligomerization process can comprise:a) preparing a catalyst system; b) allowing the catalyst system to agefor a period of time; c) contacting the aged catalyst system with anolefin; and d) forming an oligomer product. In some non-limitingembodiments, the oligomerization process can comprise, a) preparing acatalyst system; b) allowing the catalyst system to age for a period oftime; c) contacting the aged catalyst system with an olefin andhydrogen; and d) forming an oligomer product. The catalyst system,olefin, and other features of the oligomer product are independentlydescribed herein and can be utilized, without limitation to furtherdescribe the oligomerization process. In some embodiments, the catalystsystem can be prepared in a first solvent. In an embodiment, the olefin,aged catalyst system, and optionally hydrogen, can be contacted in asecond solvent. Generally, a solvent in which the catalyst system can beprepared and the solvent in which the olefin and aged catalyst systemcan be contacted can be the same; or alternatively, can be different.The catalyst system, features of aging the catalyst system, features ofthe oligomer product, and features of the impacts of aging the catalystsystem, among other features, are independently described herein and canbe utilized, without limitation to further describe the oligomerizationprocess. In some embodiments, the first and second solvent can be thesame; or alternatively, the first and second solvent can be different.

In a non-limiting embodiment, the process can comprise: a) forming acatalyst system mixture comprising an N²-phosphinyl formamidine metalsalt complex and metal alkyl; b) aging the catalyst system mixture; c)contacting the aged catalyst system mixture with an olefin; and c)forming an oligomer product. In another non-limiting embodiment, theprocess can comprise: a) forming a catalyst system mixture comprising anN²-phosphinyl formamidine compound, a metal salt, and a metal alkyl; b)aging the catalyst system mixture; c) contacting the aged catalystsystem mixture with an olefin; and c) forming an oligomer product. Insome embodiments the catalyst system mixture can further comprise asolvent (e.g. a first solvent). In some embodiments, the catalyst systemmixture and the olefin can be contacted in a solvent (e.g. a secondsolvent). In yet another non-limiting embodiment, the process cancomprise: a) forming a catalyst system mixture comprising (or consistingessentially of) an N²-phosphinyl formamidine metal salt complex, a metalalkyl, and a first solvent; b) aging the catalyst system mixture; c)contacting the aged catalyst system mixture with an olefin and a secondsolvent; and c) forming an oligomer product. In a further non-limitingembodiment, the process can comprise: a) forming a catalyst systemmixture comprising (or consisting essentially of) an N²-phosphinylformamidine compound, a metal salt, a metal alkyl, and a first solvent;b) aging the catalyst system mixture; c) contacting the aged catalystsystem mixture with an olefin and a second solvent; and d) forming anoligomer product.

In some embodiments, the step of contacting the aged catalyst systemmixture with the olefin (and optionally a solvent—e.g. second solvent)can be a step of contacting the aged catalyst system mixture with anolefin and hydrogen. The N²-phosphinyl formamidine compound, metal salt,the metal salt, N²-phosphinyl formamidine metal salt complex, the metalalkyl, the olefin, solvents, features of aging the catalyst system,features of the oligomer product, and features of the impacts of agingthe catalyst system, among other features, are independently describedherein and can be utilized, without limitation to further describe theoligomerization process. In some embodiments, the first and secondsolvent can be the same; or alternatively, the first and second solventcan be different. In some embodiments, the metal alkyl can comprise analuminoxane. Ratios for the N²-phosphinyl formamidine compound to metalsalt and ratios for the metal of the metal alkyl to metal of the metalsalt or the metal of the N²-phosphinyl formamidine metal salt complex,among other features, are independently described herein and can beutilized without limitation to further describe the oligomerizationprocess.

In an embodiment, the catalyst system (or catalyst system mixture) canbe aged for up 14 days; alternatively, up to 10 days; alternatively, upto 8 days; alternatively, up to 6 days; alternatively, up to 4 days;alternatively, up to 3 days; alternatively, up to 48 hours;alternatively, up to 36 hours; alternatively, up to 24 hours;alternatively, up to 18 hours; alternatively, up to 10 hours;alternatively, up to 8 hours; alternatively, up to 6 hours;alternatively, up to 4 hours; or alternatively, up to 3 hours. In anembodiment, the catalyst system (or catalyst system mixture) can be agedfor at least 15 minutes; alternatively, at least 20 minutes; oralternatively, at least 30 minutes. In an embodiment, the catalystsystem (or catalyst system mixture) can be aged for a time ranging fromany catalyst system (or catalyst system mixture) aging minimum timedisclosed herein to any catalyst system (or catalyst system mixture)aging maximum time disclosed herein. In some non-limiting embodiments,the catalyst system (or catalyst system mixture) can be aged for from 15minutes to 14 days; alternatively, from 15 minutes to 10 days;alternatively, from 15 minutes to 8 days; alternatively, from 15 minutesto 6 days; alternatively, from 20 minutes to 4 days; alternatively, from20 minutes to 3 days; alternatively, from 30 minutes to 48 hours;alternatively, from 30 minutes to 36 hours; alternatively, from 30minutes to 24 hours; alternatively, from 30 minutes to 18 hours;alternatively, from 30 minutes to 10 hours; alternatively, from 30minutes to 8 hours; alternatively, from 30 minutes to 6 hours;alternatively, from 30 minutes to 4 hours; or alternatively, from 30minutes to 3 hours. Other catalyst system (or catalyst system mixture)aging ranges are readily apparent from the present disclosure.

In an embodiment, any catalyst system (or catalyst system mixture)described herein can be aged at ambient temperature (15° C.-35° C.—noexternal heat source). In other embodiments, any catalyst system (orcatalyst system mixture) described herein can be aged at a temperaturefrom 10° C. to 130° C.; alternatively, from 25° C. to 100° C.;alternatively, from 30° C. to 80° C.; or alternatively, from 35° C. to60° C. In some embodiments, any catalyst system (or catalyst systemmixture) described herein can be aged under an inert atmosphere.Generally, one will recognize that the temperature at which the catalystsystem (or catalyst system mixture) is aged can have an impact upon thetime necessary to achieve an increase in catalyst system activity and/orreduction in catalyst system polymer production. In any aspect orembodiment, the catalyst system (or catalyst system mixture) can be agedat a combination of any catalyst system aging time described herein andany aging catalyst system aging temperature described herein.

The catalytic activity (oligomerization or polymerization) of anycatalyst system (or catalyst system mixture) described herein comprisingi) an N²-phosphinyl formamidine metal salt complex and metal alkyl orii) an N²-phosphinyl formamidine compound, metal salt described hereincan be defined as the grams of product produced per gram of metal of themetal salt in the N²-phosphinyl formamidine metal salt complex and ismeasured over 30 minutes beginning from when complete catalyst system iscontacted with the olefin. In an embodiment, any aged catalyst system(or catalyst system mixture) described herein (using any aging timeperiod described herein and/or any aging temperature described herein)can increase the oligomerization or polymerization activity of thecatalyst system by at least 10%; alternatively, at least 20%;alternatively, at least 30%; alternatively, at least 40%; oralternatively, at least 50%. In some embodiments, any aged catalystsystem (or catalyst system mixture) described herein (using any agingtime period described herein and/or any aging temperature describedherein) can increase the oligomerization or polymerization activity ofthe catalyst system from 10 to 1000%; alternatively, from 20 to 800%;alternatively, from 30 to 600%; alternatively, from 40 to 500%; oralternatively, from 50 to 400%. Generally, the increase in theoligomerization or polymerization catalyst system activity as a resultof aging the catalyst system (or catalyst system mixture) is determinedby comparing the activity of the aged catalyst system to the activity ofa catalyst system that has been aged for less than 12 minutes.

In an embodiment, any aged catalyst system (or catalyst system mixture)described herein (using any aging time period described herein and/orany aging temperature described herein) can provide a catalyst system(or catalyst system mixture) which can produce a reduction in thepercentage of polymer produced in an oligomerization process describedherein. In some embodiments, aging of any catalyst system (or catalystsystem mixture) described herein can reduce (using any aging time perioddescribed herein and/or any aging temperature described herein) theamount of polymer produced in an oligomerization process by at least 5%;alternatively, at least 7.5%; alternatively, at least 10%;alternatively, at least 12.5%; or alternatively, at least 15%. In someembodiments, aging of any catalyst system described herein (for any timeperiod described herein) can reduce the amount of polymer produced in anoligomerization by at least 20%; alternatively at least 25%;alternatively, at least 30%; or alternatively, at least 35%. Generally,the decrease in the catalyst system polymer production in anoligomerization process as a result of aging can be determined bycomparing the polymer production of the aged catalyst system to thepolymer production of a catalyst system that has been aged for less than12 minutes.

In an embodiment, aging a catalyst system described herein can have acombination of any increase in activity described herein and anyreduction in the amount of polymer produced described herein.

In an embodiment, a calibration curve can be produced depicting thecatalyst system activity and/or polymer production of any aged catalystsystem described herein in response to one or more catalyst system agingvariables (e.g. time, temperature, or time and temperature). In someembodiments the calibration curve can be depicted graphically as afunction of a catalyst system aging variable(s) (e.g. time, temperature,or time and temperature); or alternatively, the calibration curve can bedepicted as a predictive equation of a catalyst system aging variable(s)(e.g. time, temperature, or time and temperature). The graphicalrepresentation and/or predictive equation relating catalyst systemactivity and/or polymer production in response to catalyst aging can beutilized to adjust one or more user and/or process parameters based uponthe interpolation or extrapolation of the graphical representation orpredictive equation. It is contemplated that in some aspects, the extentto which the catalyst system activity increases and/or the extent towhich there is a decrease in polymer production with respect to catalystsystem aging can fall outside the instantly disclosed ranges and can belarger than would be expected based on the presently disclosed valuesdepending on the conditions under which the catalyst system is aged. Forexample, the catalyst system can be subjected to aging for time periodsthat are longer than those presently recited and/or at temperaturesgreater than those presently recited. The effects of aging the catalystsystem under such conditions can be subject to the herein mentionedanalysis to provide predictive information that can lead one toconditions under which catalyst system aging increases the catalystsystem activity and/or reduces the polymer production in theoligomerization process to within some user and/or process desired rangeof values. It is contemplated that given the benefits of this disclosureand using routine experimentation one having ordinary skill in the artcan modify the methodologies disclosed herein to alter the catalyticsystem activity of a disclosed catalyst system and/or reduce the amountof polymer produced in an oligomerization process to a desired value orrange. Such modifications fall within the scope of this disclosure.

In embodiments where the metal alkyl is an alumoxane, aging thealumoxane can improve aspects of the oligomerization. For example, agingthe alumoxane prior to its contact with the other components of thecatalyst system can decrease the amount of polymer produced in anoligomerization process. In some embodiments, any process for preparingthe catalyst system described herein and/or any oligomerization processdescribed herein can include a step (or steps) for aging an alumoxane.

In an embodiment, the alumoxane can be aged at ambient temperature (15°C.-35° C.—no external heat source) for at least 60 days; at least 120days; at least 180 days; or at least 240 days. In some embodiments, thealumoxane can be aged for up to 1,440 days; up to 1080 days; up to 900days; or up to 720 days. In some embodiments, the alumoxane can be agedat ambient temperature (15° C.-35° C.—no external heat source) from 60days to 1,440 days; from 120 days to 1080 days; from 180 to 900 days; orfrom 240 days to 720 days. In some embodiments, the alumoxane can beaged under an inert atmosphere.

The aging of the alumoxane can be performed at elevated temperature.Generally, aging the alumoxane at elevated temperature can reduce thetime need to achieve the benefits observed when the aged alumoxane isutilized in a catalyst system. In an embodiment, the alumoxane can beaged at a temperature from 30° C. to 100° C., from 35° C. to 90° C.,from 40° C. to 80° C., or from 45° C. to 70° C. In an embodiment, thealumoxane can be aged at any elevated temperature disclosed herein forat least 12 hours, at least 18 hours, at least 24 hours, or at least 36hours. In an embodiment, the alumoxane can be aged at any elevatedtemperature disclosed herein for up to 360 days, up to 270 days, upto180 days, or up to 90 days. In some embodiments, the alumoxane can beaged under an inert atmosphere. In an embodiment, the alumoxane can beaged for a time ranging from any alumoxane aging minimum time disclosedherein to any alumoxane aging maximum time disclosed herein. In someembodiments, the alumoxane can be aged at any elevated temperaturedisclosed herein and any alumoxane aging time disclosed herein. In anon-limiting example the alumoxane can be aged at any elevatedtemperature disclosed herein for a time ranging from 12 hours to 360days; alternatively, from 12 hours to 270 days; alternatively, from 18hours to 270 days; or alternatively, from 18 hours to 180 days. Otheralumoxane aging times at elevated temperatures are readily apparent fromthe present disclosure. In some embodiments, the alumoxane can be agedunder an inert atmosphere.

In an embodiment, aging of the alumoxane can provide a reduction in thepercentage of polymer produced by the oligomerization process. In someembodiments, aging of the alumoxane can reduce the amount of polymerproduced in an oligomerization process by at least 20%; at least 40%; atleast 60%; at least 70%; at least 75%; at least 80%; or at least 85%.

In an embodiment, a calibration curve can be produced depicting thecatalyst system polymer production utilizing an aged alumoxane inresponse to one or more alumoxane aging variables (e.g. time,temperature, or time and temperature). In some embodiments the alumoxaneaging calibration curve can be depicted graphically as a function of analumoxane aging variable(s) (e.g. time, temperature, or time andtemperature); alternatively, the calibration curve can be depicted as apredictive equation of an alumoxane aging variable(s) (e.g. time,temperature, or time and temperature). The graphical representationand/or predictive equation relating catalyst system polymer productionin response to alumoxane aging can be utilized to adjust one or moreuser and/or process parameters based upon the interpolation orextrapolation of the graphical representation or predictive equation. Itis contemplated that in some aspects, the extent to which the polymerproduction of the catalyst system decreases with respect to alumoxaneaging can fall outside the instantly disclosed ranges and can be largerthan would be expected based on the presently disclosed values dependingon the conditions under which alumoxane is aged. For example, thecatalyst system can be subjected to aging for time periods that arelonger than those presently recited and/or at temperatures greater thanthose presently recited. The effects of alumoxane aging under suchconditions can be subject to the herein mentioned analysis to providepredictive information that can lead to conditions under which alumoxaneaging can reduce the polymer production of the catalyst system in theoligomerization process. It is contemplated that given the benefits ofthis disclosure and using routine experimentation one having ordinaryskill in the art can modify the methodologies disclosed herein to altera reduction in the amount of polymer produced in an oligomerizationprocess. Such modifications fall within the scope of this disclosure.

Substituent Groups

Various aspect and embodiments described herein refer to non-hydrogensubstituents such as halogen (or halo, halide), hydrocarbyl,hydrocarboxy, alkyl, and/or alkoxy substituents. In an embodiment, eachnon-hydrogen substituent of any aspect or embodiment calling for a substituent can be a halogen, a hydrocarbyl group, or a hydrocarboxy group;alternatively, a halogen or a hydrocarbyl group; alternatively, ahalogen or a hydrocarboxy group; alternatively, a hydrocarbyl group or ahydrocarboxy group; alternatively, a halogen; alternatively, ahydrocarbyl group; or alternatively, a hydrocarboxy group. In anembodiment, each hydrocarbyl substituent can be a C₁ to C₁₀ hydrocarbylgroup; or alternatively, a C₁ to C₅ hydrocarbyl group. In an embodiment,each hydrocarboxy substituent of any aspect or embodiment calling for asubstituent can be a C₁ to C₁₀ hydrocarboxy group; or alternatively, aC₁ to C₅ hydrocarboxy group. In an embodiment, any halide substituent ofany aspect or embodiment calling for a substituent can be a fluoride,chloride, bromide, or iodide; alternatively, a fluoride or chloride. Insome embodiments, any halide substituent of any aspect or embodimentcalling for a substituent can be a fluoride; alternatively, a chloride;alternatively, a bromide; or alternatively, an iodide.

In an embodiment, any hydrocarbyl substituent of any aspect orembodiment calling for a substituent can be an alkyl group, an arylgroup, or an aralkyl group; alternatively, an alkyl group;alternatively, an aryl group; or alternatively, an aralkyl group. In anembodiment, any alkyl substituent of any aspect or embodiment callingfor a substituent can be a methyl group, an ethyl group, an n-propylgroup, an isopropyl group, an n-butyl group, a sec-butyl group, anisobutyl group, a tert-butyl group, an n-pentyl group, a 2-pentyl group,a 3-pentyl group, a 2-methyl-1-butyl group, a tert-pentyl group, a3-methyl-1-butyl group, a 3-methyl-2-butyl group, or a neo-pentyl group;alternatively, a methyl group, an ethyl group, an isopropyl group, atert-butyl group, or a neo-pentyl group; alternatively, a methyl group;alternatively, an ethyl group; alternatively, an isopropyl group;alternatively, a tert-butyl group; or alternatively, a neo-pentyl group.In an embodiment, any aryl substituent of any aspect or embodimentcalling for a substituent can be phenyl group, a tolyl group, a xylylgroup, or a 2,4,6-trimethylphenyl group; alternatively, a phenyl group;alternatively, a tolyl group, alternatively, a xylyl group; oralternatively, a 2,4,6-trimethylphenyl group. In an embodiment, anyaralkyl substituent of any aspect or embodiment calling for asubstituent can be benzyl group or an ethylphenyl group(2-phenyleth-1-yl or 1-phenyleth-1-yl); alternatively, a benzyl group;alternatively, an ethylphenyl group; alternatively a 2-phenyleth-1-ylgroup; or alternatively, a 1-phenyleth-1-yl group.

In an embodiment, any hydrocarboxy substituent of any aspect orembodiment calling for a substituent can be an alkoxy group, an aryloxygroup, or an aralkoxy group; alternatively, an alkoxy group;alternatively, an aryloxy group, or an aralkoxy group. In an embodiment,any alkoxy substituent of any aspect or embodiment calling for asubstituent can be a methoxy group, an ethoxy group, an n-propoxy group,an isopropoxy group, an n-butoxy group, a sec-butoxy group, an isobutoxygroup, a tert-butoxy group, an n-pentoxy group, a 2-pentoxy group, a3-pentoxy group, a 2-methyl-1-butoxy group, a tert-pentoxy group, a3-methyl-1-butoxy group, a 3-methyl-2-butoxy group, or a neo-pentoxygroup; alternatively, a methoxy group, an ethoxy group, an isopropoxygroup, a tert-butoxy group, or a neo-pentoxy group; alternatively, amethoxy group; alternatively, an ethoxy group; alternatively, anisopropoxy group; alternatively, a tert-butoxy group; or alternatively,a neo-pentoxy group. In an embodiment, any aryloxy substituent of anyaspect or embodiment calling for a substituent can be phenoxy group, atoloxy group, a xyloxy group, or a 2,4,6-trimethylphenoxy group;alternatively, a phenoxy group; alternatively, a toloxy group,alternatively, a xyloxy group; or alternatively, a2,4,6-trimethylphenoxy group. In an embodiment, any aralkoxy substituentof any aspect or embodiment calling for a substituent can be benzoxygroup.

Solvents

The methods described herein can utilize one or more solvents. Solventswhich can be utilized in aspects of the present disclosure includewithout limitation water, hydrocarbons, halogenated hydrocarbons,ethers, carbonates, esters, ketones, aldehydes, alcohols, nitriles andcombinations thereof. In some embodiments, an aspect of the presentdisclosure can call for a polar solvent. Polar solvents which can beutilized include without limitation water ethers, carbonates, esters,ketones, aldehydes, alcohols, nitriles, and mixtures thereof;alternatively, ethers, carbonates, esters, ketones, aldehydes, alcohols,nitriles, and mixtures thereof; alternatively, ethers, esters, ketones,alcohols, nitriles, and mixtures thereof; alternatively, ethers;alternatively, carbonates; alternatively, esters; alternatively,ketones; alternatively, aldehydes; alternatively, alcohols; oralternatively, nitriles. In some embodiments, an aspect of the presentdisclosure can call for an aprotic polar solvent. Aprotic polar solventswhich can be utilized include without limitation ethers, esters,ketones, aldehydes, nitriles, and mixtures thereof; alternatively,ethers, nitriles and mixtures thereof; alternatively, esters, ketones,aldehydes and mixtures thereof; alternatively, ethers; alternatively,esters; alternatively, ketones; alternatively, aldehydes; oralternatively, nitriles. In other embodiments, an aspect of thedisclosure can call for a non-polar solvent. Non-polar solvents includewithout limitation hydrocarbons, halogenated hydrocarbons, or mixturesthereof; alternatively, a hydrocarbon; or alternatively, a halogenatedhydrocarbon. In another embodiment, an aspect of the present disclosurecan call for a solvent that is substantially unreactive with a metalalkyl. Solvents which are unreactive with a metal alkyl include withoutlimitation ethers, hydrocarbons, and mixtures thereof; alternatively,ethers; or alternatively, hydrocarbons.

Hydrocarbons and halogenated hydrocarbon can include, for example,aliphatic hydrocarbons, aromatic hydrocarbons, petroleum distillates,halogenated aliphatic hydrocarbons, halogenated aromatic hydrocarbons,or combinations thereof; alternatively aliphatic hydrocarbons, aromatichydrocarbons, halogenated aliphatic hydrocarbons, halogenated aromatichydrocarbons, and combinations thereof; alternatively, aliphatichydrocarbons; alternatively, aromatic hydrocarbons; alternatively,halogenated aliphatic hydrocarbons; or alternatively, halogenatedaromatic hydrocarbons. Aliphatic hydrocarbons which can be useful as asolvent include C₃ to C₂₀ aliphatic hydrocarbons; alternatively C₄ toC₁₅ aliphatic hydrocarbons; or alternatively, C₅ to C₁₀ aliphatichydrocarbons. The aliphatic hydrocarbons can be cyclic or acyclic and/orcan be linear or branched, unless otherwise specified. Non-limitingexamples of suitable acyclic aliphatic hydrocarbon solvents that can beutilized singly or in any combination include propane, iso-butane,n-butane, butane (n-butane or a mixture of linear and branched C₄acyclic aliphatic hydrocarbons), pentane (n-pentane or a mixture oflinear and branched C₅ acyclic aliphatic hydrocarbons), hexane (n-hexaneor mixture of linear and branched C₆ acyclic aliphatic hydrocarbons),heptane (n-heptane or mixture of linear and branched C₇ acyclicaliphatic hydrocarbons), octane (n-octane or a mixture of linear andbranched C₈ acyclic aliphatic hydrocarbons), and combinations thereof;alternatively, iso-butane, n-butane, butane (n-butane or a mixture oflinear and branched C₄ acyclic aliphatic hydrocarbons), pentane(n-pentane or a mixture of linear and branched C₅ acyclic aliphatichydrocarbons), hexane (n-hexane or mixture of linear and branched C₆acyclic aliphatic hydrocarbons), heptane (n-heptane or mixture of linearand branched C₇ acyclic aliphatic hydrocarbons), octane (n-octane or amixture of linear and branched C₈ acyclic aliphatic hydrocarbons), andcombinations thereof; alternatively, iso-butane, n-butane, butane(n-butane or a mixture of linear and branched C₄ acyclic aliphatichydrocarbons), pentane (n-pentane or a mixture of linear and branched C₅acyclic aliphatic hydrocarbons), heptane (n-heptane or mixture of linearand branched C₇ acyclic aliphatic hydrocarbons), octane (n-octane or amixture of linear and branched C₈ acyclic aliphatic hydrocarbons), andcombinations thereof; alternatively, propane; alternatively, iso-butane;alternatively, n-butane; alternatively, butane (n-butane or a mixture oflinear and branched C₄ acyclic aliphatic hydrocarbons); alternatively,pentane (n-pentane or a mixture of linear and branched C₅ acyclicaliphatic hydrocarbons); alternatively, hexane (n-hexane or mixture oflinear and branched C₆ acyclic aliphatic hydrocarbons); alternatively,heptane (n-heptane or mixture of linear and branched C₇ acyclicaliphatic hydrocarbons); or alternatively, octane (n-octane or a mixtureof linear and branched C₈ acyclic aliphatic hydrocarbons). Non-limitingexamples of suitable cyclic aliphatic hydrocarbon solvents includecyclohexane, methyl cyclohexane; alternatively cyclohexane; oralternatively, methylcyclohexane. Aromatic hydrocarbons which can beuseful as a solvent include C₆ to C₂₀ aromatic hydrocarbons; oralternatively, C₆ to C₁₀ aromatic hydrocarbons. Non-limiting examples ofsuitable aromatic hydrocarbons that can be utilized singly or in anycombination include benzene, toluene, xylene (including ortho-xylene,meta-xylene, para-xylene, or mixtures thereof), and ethylbenzene, orcombinations thereof; alternatively, benzene; alternatively, toluene;alternatively, xylene (including ortho-xylene, meta-xylene, para-xyleneor mixtures thereof); or alternatively, ethylbenzene.

Halogenated aliphatic hydrocarbons which can be useful as a solventinclude C₁ to C₁₅ halogenated aliphatic hydrocarbons; alternatively, C₁to C₁₀ halogenated aliphatic hydrocarbons; or alternatively, C₁ to C₅halogenated aliphatic hydrocarbons. The halogenated aliphatichydrocarbons can be cyclic or acyclic and/or can be linear or branched,unless otherwise specified. Non-limiting examples of suitablehalogenated aliphatic hydrocarbons which can be utilized includemethylene chloride, chloroform, carbon tetrachloride, dichloroethane,trichloroethane, and combinations thereof; alternatively, methylenechloride, chloroform, dichloroethane, trichloroethane, and combinationsthereof; alternatively, methylene chloride; alternatively, chloroform;alternatively, carbon tetrachloride; alternatively, dichloroethane; oralternatively, trichloroethane. Halogenated aromatic hydrocarbons whichcan be useful as a solvent include C₆ to C₂₀ halogenated aromatichydrocarbons; or alternatively, C₆ to C₁₀ halogenated aromatichydrocarbons. Non-limiting examples of suitable halogenated aromatichydrocarbons include chlorobenzene, dichlorobenzene, and combinationsthereof; alternatively chlorobenzene and dichlorobenzene.

Ethers, carbonates, esters, ketones, aldehydes, or alcohols which can beuseful as a solvent include C₂ to C₂₀ ethers, carbonates, esters,ketones, aldehydes, or alcohols; alternatively, C₂ to C₁₀ ethers,carbonates, esters, ketones, aldehydes, or alcohols; or alternatively,C₂ to C₅ ethers, carbonates, esters, ketones, aldehydes, or alcohols.Suitable ether solvents can be cyclic or acyclic. Non-limiting examplesof suitable ethers which can be useful as a solvent include dimethylether, diethyl ether, methyl ethyl ether, monoethers or diethers ofglycols (e.g., dimethyl glycol ether), furans, substituted furans,dihydrofuran, substituted dihydrofurans, tetrahydrofuran (THF),substituted tetrahydrofurans, tetrahydropyrans, substitutedtetrahydropyrans, 1,3-dioxanes, substituted 1,3-dioxanes, 1,4-dioxanes,substituted 1,4-dioxanes, or mixtures thereof. In an embodiment, eachsubstituent of a substituted furan, substituted dihydrofuran,substituted tetrahydrofuran, substituted tetrahydropyran, substituted1,3-dioxane, or substituted 1,4-dioxane, can be a C₁ to C₅ alkyl group.C₁ to C₅ alkyl substituent group are disclosed herein and can beutilized without limitation of further describe the substitutedtetrahydrofuran, dihydrofuran, furan, 1,3-dioxane, or 1,4 dioxanesolvents. Non-limiting examples of suitable carbonates which can beutilized as a solvent include ethylene carbonate, propylene carbonate,diethyl carbonate, diethyl carbonate, glycerol carbonate, andcombinations thereof. Non-limiting examples of suitable esters which canbe utilized as a solvent include ethyl acetate, propyl acetate, butylacetate, isobutyl isobutyrate, methyl lactate, ethyl lactate, andcombinations thereof. Non-limiting examples of suitable ketones whichcan be utilized as a solvent include acetone, ethyl methyl ketone,methyl isobutyl ketone, and combinations thereof. Non-limiting examplesof suitable alcohols which can be utilized as a solvent includemethanol, ethanol, propanol, isopropanol, n-butanol, isobutanol,pentanol, hexanol, heptanol, octanol, benzyl alcohol, phenol,cyclohexanol, and the like, or combinations thereof.

General Disclosure Information

For the purpose of any U.S. national stage filing from this application,all publications and patents mentioned in this disclosure areincorporated herein by reference in their entireties, for the purpose ofdescribing and disclosing the constructs and methodologies described inthose publications, which might be used in connection with the methodsof this disclosure. Any publications and patents discussed above andthroughout the text are provided solely for their disclosure prior tothe filing date of the present application. Nothing herein is to beconstrued as an admission that the inventors are not entitled toantedate such disclosure by virtue of prior invention.

In any application before the United States Patent and Trademark Office,the Abstract of this application is provided for the purpose ofsatisfying the requirements of 37 C.F.R. § 1.72 and the purpose statedin 37 C.F.R. § 1.72(b) “to enable the United States Patent and TrademarkOffice and the public generally to determine quickly from a cursoryinspection the nature and gist of the technical disclosure.” Therefore,the Abstract of this application is not intended to be used to construethe scope of the claims or to limit the scope of the subject matter thatis disclosed herein. Moreover, any headings that can be employed hereinare also not intended to be used to construe the scope of the claims orto limit the scope of the subject matter that is disclosed herein. Anyuse of the past tense to describe an example otherwise indicated asconstructive or prophetic is not intended to reflect that theconstructive or prophetic example has actually been carried out.

The present disclosure is further illustrated by the following examples,which are not to be construed in any way as imposing limitations uponthe scope thereof. On the contrary, it is to be clearly understood thatresort can be had to various other aspects, embodiments, modifications,and equivalents thereof which, after reading the description herein, cansuggest themselves to one of ordinary skill in the art without departingfrom the spirit of the present invention or the scope of the appendedclaims.

The data and descriptions provided in the following examples are givento show particular aspects and embodiments of the compounds, catalystsystems, and oligomerization and/or polymerization methods disclosed,and to demonstrate a number of the practices and advantages thereof. Theexamples are given as a more detailed demonstration of some of theaspects and embodiments described herein and are not intended to limitthe disclosure or claims in any manner.

EXAMPLES

Unless otherwise stated, all operations were carried out under argon ina glove box or using standard Schlenk techniques. Tetrahydrofuran anddiethyl ether were purified by standard drying procedures and distilled(under argon) from sodium/benzophenone prior to use. All other solventswere purchased in anhydrous form, degassed prior to use and stored overactivated molecular sieves in a glovebox. All chemical reagents werepurchased from commercial sources and used as received. Proton NMRspectra were obtained on a Bruker AVANCE 11400 MHz spectrometeroperating at room temperature.

Synthesis of Hydrocarboxymethanimine Compounds HydrocarboxymethanimineSynthesis 1—(E)-N-(2-ethylphenyl)methoxymethanimine (HMA I)

To a dry 100 mL Schlenk flask was added 50 mL of anhydrous benzene, 6.1mL (50 mmoles) 2-ethylaniline, 11.0 mL (100 mmoles)trimethylorthoformate, and 80 mg p-toluenesulfonic acid monohydrate(catalyst). The solution became clear orange and was refluxed for twelvehours, during which it became a darker clear orange solution. Volatileswere removed under vacuum leaving an orange oil. This oil was heatedunder vacuum and a clear oil was distilled (60° C., 0.1 Torr), yielding3.76 grams (46.1 mole % yield) of the desired product. ¹H NMR (400 MHz,CDCl₃): δ=7.66, s, 1H (N═CH); 7.18, d, 1H; 7.11, m, 2H; 6.75, d, 2H;3.89, s, 3H (OMe); 2.65, q, 2H (2-CH₂CH₃); 1.17, t, 3H (2-CH₂CH₃).

Hydrocarboxymethanimine Synthesis2—(E)-N-(2,6-dimethylphenyl)methoxymethanimine (HMA II)

To a dry 100 mL Schlenk flask was added 50 mL of anhydrous benzene, 6.2mL (50 mmoles) 2,6-dimethylaniline, 11.0 mL (100 mmoles)trimethylorthoformate, and 80 mg p-toluenesulfonic acid monohydrate(catalyst). The solution became clear and was refluxed for twelve hours,during which there was no observed color change. Volatiles were removedunder vacuum leaving a cloudy white oil. This oil was heated undervacuum and a clear oil was distilled (60° C., 0.1 Torr), yielding 4.90grams (66.1 mole % yield) of the desired product. ¹H NMR (400 MHz,CDCl3): δ=7.51, s, 1H (N═CH); 7.01, d, 2H; 6.89, t, 1H; 3.94, s, 3H(OMe); 2.16, s, 6H (2,6-di-CH3).

Hydrocarboxymethanimine Synthesis3—(E)-N-(2-tert-butylphenyl)methoxymethanimine (HMAIII)

To a dry 100 ml Schlenk flask was added 50 mL of anhydrous benzene, 6.0ml (38.5 mmoles) 2-t-butylaniline, 8.5 ml (77.0 mmoles)trimethylorthoformate, and 80 mg p-tolusulfonic acid monohydrate(catalyst). The solution became clear red and was refluxed for twelvehours, during which there was no observed color change. Volatiles wereremoved under vacuum leaving an orange oil. This oil was heated undervacuum and a clear oil was distilled {60° C., 0.1 Torr), yielding 5.54grams (75.3 mole % yield) of the desired product. ¹H NMR (400 MHz,CDCb): δ=7.62, s, 1H (N═CH); 7.35, d, 1H; 7.14, t, 1H; 7.07, t, 1H;6.68, d, 1H; 3.92, s, 3H (OMe); 1.41, s, 9H (2-C(CH₃)₃).

TABLE I Hydrocarboxymethanimine Compounds

HMA I

HMA II

HMA III

Synthesis of Formamidine Compounds Formamidine Synthesis1—(E)-N-(2,6-dimethylphenyl)formamidine (FA I)

(E)-N-(2,6-dimethylphenyl)methoxymethanimine, HMA II, (4.90 grams, 30.03mmoles) and 1.44 grams (15.12 mmoles) ammonium carbonate were added to adry 100 mL Schlenk flask containing 50 mL methanol. The solution becameclear and was stirred for twelve hours, during which no color change wasobserved. Volatiles were removed by vacuum, leaving a white solid. Thissolid was heated under vacuum and a clear oil was distilled (60° C., 0.1Torr), yielding 3.07 grams (69.1 mole % yield) of a white solid. ¹H NMR(400 MHz, CDCl₃): δ=7.29, s, 1H (N═CH); 7.00, d, 2H; 6.87, t, 1H; 4.42,broad singlet, 2H (NH₂); 2.13, s, 6H (2,6-di-CH₃).

Formamidine Synthesis 2—(E)-N,N′-bis(2-ethylphenyl)formamidine (FA II)

To a dry 50 mL Schlenk flask was added 25 mL of anhydrous benzene, 1.1mL (10 mmoles) of trimethylorthoformate, 2.5 mL (20 mmoles) of2-ethylaniline, and 80 mg p-toluenesulfonic acid monohydrate (catalyst).The solution became clear red and was refluxed for twelve hours. Themixture was cooled, treated with saturated aqueous NaHCO₃, and extractedwith 2×20 mL benzene. The combined benzene layers were dried with Na₂S0₄and filtered. Benzene was removed under vacuum leaving an orange solid.The solid was heated at 60° C. under vacuum to remove unreacted anilinevia distillation (0.1 Torr). An orange solid remained (1.60 grams, 63.5mole % yield). ¹H NMR (400 MHz, CDCl₃): δ=8.04, s, 1H (N═CH); 7.19, m,4H; 7.05, m, 4H; 6.75, d, 2H; 2.68, q, 4H (2-CH₂CH₃); 1.24, t, 6H(2-CH₂CH₃).

(E)-N, N′-bis(phenyl)formamidine (Formamidine compound FA III),(E)-N,N′-bis(4-tert-butylphenyl)formamidine (Formamidine compound FAIV), and (E)-N,N′-bis(2,6-dimethylphenyl)-formamidine (Formamidinecompound FA V) were prepared according to the procedure of FormamidineSynthesis 2 using the appropriate amine and the appropriate molarratios. (E)-N-(2,5-di-tert-butylphenyl)formamidine (Formidine compoundFA VI) was prepared according to the procedure of Formamidine Synthesis2 using the appropriate hydrocarboxymethanimine (prepared using theappropriate amine and the procedure of HydrocarboxylmethanimineSynthesis 1) and the appropriate molar ratios.

TABLE II Formamidine Compounds

FA I

FA II

FA III

FA IV

FA V

FA VI

Synthesis of N²-Phosphinyl Formamidine Compounds PhosphinylformamidineSynthesis1—(E)-N′-(2,6-dimethylphenyl)-N-(diisopropylphosphinyl)-formamidine (NPI)

(E)-N-(2,6-dimethylphenyl)formamidine, FA I, (0.74 grams, 5.0 mmoles)was dissolved in 50 mL of diethyl ether, cooled to 0° C., and treateddropwise with 2.5 mL (5.0 mmoles) of 2.0 M butyllithium in pentane. Thecolor changed instantly from clear to cloudy white. The mixture wasstirred for three hours at room temperature and treated with 0.80 mL(5.0 mmoles) chlorodiisopropylphosphine. This mixture was stirred for anadditional hour at room temperature resulting in a cloudy white slurry.Filtration through diatomaceous earth and removal of volatiles undervacuum provided a thick pale yellow oil (0.7995 grams, 60.5 mole %yield).

Phosphinylformamidine Synthesis2—(E)-N′-(2,6-dimethylphenyl)-N-(diphenylphosphinyl)formamidine (NP II)

(E)-N-(2,6-dimethylphenyl)formamidine, FA I, (0.74 grams, 5.0 mmoles)was dissolved in 50 mL of diethyl ether, cooled to 0° C., and treateddropwise with 2.5 mL (5.0 mmoles) of 2.0 M butyllithium in pentane. Thecolor changed instantly from clear to cloudy white. The mixture wasstirred for three hours at room temperature and treated with 0.90 mL(5.0 mmoles) chlorodiphenylphosphine. This mixture was stirred for anadditional hour at room temperature resulting in a cloudy white slurry.Filtration through diatomaceous earth and removal of volatiles undervacuum provided a quantitative yield of thick pale white oil.

Phosphinylformamidine Synthesis3—(E)-N,N′-bis(2-ethylphenyl)-N-(diisopropylphosphinyl)-formamidine (NPIII)

(E)-N,N′-bis(2-ethylphenyl)formamidine, FA II, (0.656 g, 2.6 mmol) wasdissolved in 50 mL of diethyl ether, cooled to 0° C., and treateddropwise with 1.3 mL (2.6 mmol) of 2.0 M butyllithium in pentane. Thecolor changed instantly from pale orange to pale green. The mixture wasstirred for three hours at room temperature and treated with 0.40 mL(2.6 mmol) of chlorodiisopropylphosphine. This mixture was stirred foran additional hour at room temperature resulting in a cloudy, pale greenslurry. Filtration through diatomaceous earth and removal of volatilesunder vacuum provided a clear, pale yellow oil (0.752 grams, 78.5 mole %yield).

Phosphinylformamidine Synthesis4—(E)-N,N′-bis(2-ethylphenyl)-N-(diphenylphosphinyl)formamidine (NP IV)

(E)-N,N′-bis(2-ethylphenyl)formamidine, FA II, (0.656 g, 2.6 mmol) wasdissolved in 50 mL of diethyl ether, cooled to 0° C., and treateddropwise with 1.3 mL (2.6 mmol) of 2.0 M butyllithium in pentane. Theresulting solution was stirred for three hours at room temperature,yielding a cloudy pale green slurry. Chlorodiphenylphosphine (0.47 mL,2.6 mmol) was added dropwise and the pale yellow solution was stirredfor one hour at room temperature. Filtration through diatomaceous earthand removal of volatiles provided 1.14 g (98.2 mole % yield) of paleorange oil.

(E)-N,N′-bis(phenyl)-N-(diisopropylphosphinyl)formamidine (N²Phosphinylformamidine Compound NPF V),(E)-N,N′-bis(phenyl)-N-(diphenylphosphinyl)formamidine (N²Phosphinylformamidine Compound NPF VI),(E)-N,N′-bis(4-tert-butylphenyl)-N-(diisopropylphosphinyl)-formamidine(N² Phosphinylformamidine Compound NPF VII),(E)-N,N′-bis(4-tert-butylphenyl)-N-(diphenylphosphinyl)formamidine (N²Phosphinylformamidine Compound NPF VIII),(E)-N,N′-bis(2,6-dimethylphenyl)-N-(diisopropylphosphinyl)formamidine(N² Phosphinylformamidine compound NPF IX),(E)-N,N′-bis(2,6-dimethylphenyl)-N-(diphenylphosphinyl)formamidine (N²Phosphinylformamidine Compound NPF X), and(E)-N′-(2,5-di-tert-butylphenyl)-N-(diphenylphosphinyl)formamidine (N²Phosphinylformamidine Compound NPF XI) were prepared according to theprocedure of Phosphinylformamidine Synthesis 1 using the appropriateformamidine compound, the appropriate phosphine chloride, and theappropriate molar ratios.

TABLE III N² Phosphinylformamidine Compounds

NPF I

NPF II

NPF II

NPF IV

NPF V

NPF VI

NPF VII

NPF VIII

NPF IX

NPF X

NPF XI

Synthesis of N²-Phosphinyl Formamidine Metal Salt Complexes PhosphinylFormamidine Metal Complex Synthesis1—[(E)-N′-(2,6-dimethylphenyl)-N-(diisopropylphosphino)formamidine](THF)CrCl3 (NPFMC I)

(E)-N′-(2,6-dimethylphenyl)-N-(diisopropylphosphinyl)formamidine, NP I,(0.132 grams, 0.5 mmoles) was dissolved in THF and added dropwise to asolution of THF containing 0.187 grams (0.5 mmoles) of CrCl₃(THF)₃resulting in an immediate color change from purple to blue. Thissolution was stirred for twelve hours, during which it became cloudylight blue. It was filtered and volatiles were removed by vacuum,yielding 0.145 grams (57.0 mole % yield) of a blue solid.

Phosphinyl Formamidine Metal Complex Synthesis2—[(E)-N′-(2,6-dimethylphenyl)-N-(diphenylphosphino)formamidine](THF)CrCl₃ (NPFMC II)

(E)-N′-(2,6-dimethylphenyl)-N-(diphenylphosphinyl)formamidine, (NP II,(0.166 grams, 0.5 mmoles) was dissolved in THF and added dropwise to asolution of THF containing 0.187 grams (0.5 mmoles) of CrCl₃(THF)₃resulting in an immediate color change from purple to blue. Thissolution was stirred for twelve hours and volatiles were removed byvacuum resulting in a blue solid. This solid was rinsed with pentane anddried (0.277 grams, 96.2 mole % yield).

Phosphinyl Formamidine Metal Complex Synthesis3—[(E)-N,N′-bis(2-ethylphenyl)-N-(diisopropylphosphino)formamidine](THF)CrCl₃ (NPFMC III)

(E)-N,N′-bis(2-ethylphenyl)-N-(diisopropylphosphinyl)formamidine, NPIII, (0.218 grams, 0.5 mmoles) was dissolved in THF and added dropwiseto a solution of THF containing 0.187 grams (0.5 mmoles) of CrCl₃(THF)₃.This solution was stirred for twelve hours, during which it became blue.Volatiles were removed by vacuum resulting in a blue solid. This solidwas rinsed with pentane and dried (0.251 grams, 73.6 mole % yield).

Phosphinyl Formamidine Metal Complex Synthesis4—[(E)-N,N′-bis(2-ethylphenyl)-N-(diphenylphosphino)formamidine)(THF)CrCl₃ (NPFMC IV)

(E)-N,N′-bis(2-ethylphenyl)-N-(diphenylphosphinyl)formamidine, NP IV,(0.184 grams, 0.5 mmoles) was dissolved in THF and added dropwise to asolution of THF containing 0.187 grams (0.5 mmoles) of CrCl₃(THF)₃. Thissolution was stirred for twelve hours, during which it became blue.Volatiles were removed by vacuum resulting in a blue solid. This solidwas rinsed with pentane and dried (0.222 grams, 72.3 mole % yield).

(E)-N,N′-bis(phenyl)-N-(diisopropylphosphinyl)formamidine(THF)CrCl₃ (N²Phosphinylformamidine Metal Complex NPFMC V),(E)-N,N′-bis(phenyl)-N-(diphenylphosphinyl)-formamidine (THF)CrCl₃ (N²Phosphinylformamidine Metal Complex NPFMC VI),(E)-N,N′-bis(4-tert-butylphenyl)-N-(diisopropylphosphinyl)formamidine(THF)CrCl₃ (N² Phosphinylformamidine Metal Complex NPFMC VII),(E)-N,N′-bis(4-tert-butylphenyl)-N-(diphenylphosphinyl)-formamidine(THF)CrCl₃ (N² Phosphinylformamidine Metal Complex NPFMC VIII),(E)-N,N′-bis(2,6-dimethylphenyl)-N-(diisopropylphosphinyl)formamidine(THF)CrCl₃ (N² Phosphinylformamidine Metal Complex NPFMC IX),(E)-N,N′-bis(2,6-dimethylphenyl)-N-(diphenylphosphinyl) (THF)CrCl₃ (N²Phosphinylformamidine Metal Complex NPFMC X), and(E)-N′-(2,5-di-tert-butylphenyl)-N-(diphenylphosphinyl)formamidine (N²Phosphinylformamidine Metal Complex NPFMC XI) were prepared according tothe procedure of Phosphinylformamidine Metal Complex Synthesis 1 usingthe appropriate N²-phosphinylformamidine formamidine compound, theappropriate metal salt, and the appropriate molar ratios.

TABLE IV N² Phosphinylformamidine Metal Salt Complexes (NFP FormamidineMetal Salt Complexes)

NPFMC I

NPFMC II

NPFMC III

NPFMC IV

NPFMC V

NPFMC VI

NPFMC VII

NPFMC VIII

NPFMC IX

NPFMC X

NPFMC XIOlefin Oligomerization

The N²-phosphinylformamidine metal salt complexes were utilized asprepared using the methods described herein. The MMAO-3A (7 wt. %aluminum in heptanes) was utilized as obtained from the chemicalsupplier Akzo-Nobel. The solvents were dried and/or purified usingconventional methods and stored under conditions to limit their abilityto pick-up water. In the product analyses, reference to an amount of C6or C8 products refer to all oligomer products having 6 or 8 carbonatoms, respectively, within the oligomer product. References to weightpercent of 1-hexene or 1-octene refer to the weight percent of 1-hexeneor 1-octene in the C6 or C8 product portion of the oligomer product,respectively (e.g., product purities).

Ethylene Oligomerization Run—Standard Method

A 1 L stainless steel reactor was dried under vacuum at 110° C. for atleast 8 hours prior to use. The reactor was then cooled to 50° C. In thedrybox, a 20 mL glass vial was charged with an N²-phosphinyl formamidinemetal salt complex and ethylbenzene (1.0 g). MMAO-3A was added to theblue heterogeneous solution of the N2-phosphinyl metal salt complexresulting in formation of a yellow solution. The catalyst system wasthen allowed to age a room temperature for 4 hours. The yellow solutionwas then added to 0.5 L glass charger containing cyclohexane. Thissolution was removed from the drybox and charged into the reactor.Hydrogen was added to the reactor followed by ethylene. The reaction wasallowed to proceed for 30 minutes (starting from the introduction ofethylene) at 70° C. with ethylene fed to maintain reactor pressure andheating or cooling as necessary to maintain the desired temperature.After 30 minutes, water cooling was applied to the reactor system. Oncethe temperature reached 35° C., the unreacted ethylene and hydrogen gaswas vented to the atmosphere. A liquid sample was collected and analyzedby GC-FID; for this run ethylbenzene was used as the internal standard.Solids were collected by filtering the solution and cleaning the reactorwalls and cooling coil. The N²-phosphinyl formamidine metal saltcomplexes and amount of materials utilized for each ethyleneoligomerization are provided are summarized in Table V along with theresults of each oligomerization run.

TABLE V N²-Phosphinyl Formamidine Complex, Catalyst System Ratios, andReaction Condition for Ethylene Oligomerization Runs 5-26. Run # 1 2 3 45 6 7 8 9 10 Ethylene Oligomerization Conditions Complex 8a 8a 8b 9a 10a10b 11a 11b 12a 13b Complex GMW¹ 566.91 566.91 634.95 671.06 614.96682.99 727.17 795.2 671.06 719.1 Complex Amount (mg) 7 7 7 7 7 7 7 7 7 7Cr (mg) 0.64 0.64 0.57 0.54 0.59 0.53 0.50 0.46 0.54 0.51 Al:Cr molarratio 600 600 700 700 600 700 800 800 700 800 Cyclohexane Solvent 0.4 L0.4 L 0.4 L 0.4 L 0.4 L 0.4 L 0.4 L 0.4 L 0.4 L 0.4 L Reaction Time(min) 30 30 30 30 30 30 30 30 30 30 C₂H₄ pressure (psi) 875 875 875 875875 875 875 875 875 875 H₂ pressure (psi) 25 25 25 25 25 25 25 25 25 25Reaction Temperature 70 70 70 70 70 70 70 70 70 70 (° C.) EthyleneOligamerization Product Analysis Solid Product (g) <2 <2 <2 <2 6 <2 >2<2 <2 <2 Liquid Product (g) 339.8 316 60.7 5.8 1 0.3 6.8 0.4 4.7 116Carbon Number Distribution (wt. %) C₆ 93.7 93.9 80.6 83.9 51.6 NA 38.1NA 91.4 95.1 C₈ 0.8 0.8 18.2 5.2 26.3 NA 27.4 NA 8.1 2.4 C₁₀₊ 5.5 5.31.2 10.9 22.1 NA 34.5 NA 0.5 2.5 g(C₆ + C₈)/gCr 500,113 466,069 104,6139,527 1,316 inactive 8,898 inactive 8,621 223,435 1-hexene in C₆'s (wt.%) 99.71 99.69 99.2 96.76 5994 NA 38.16 NA 98.85 99.63 1-octene in C₈'s(wt. %) 97.74 98.01 99.64 82.89 83.13 NA 72.48 NA 95.26 98.28 ¹Assumedtwo THF neutral ligand per complex molecule.

While preferred embodiments of the invention have been shown anddescribed, modifications thereof can be made by one skilled in the artwithout departing from the spirit and teachings of the disclosure. Theembodiments described herein are exemplary only, and are not intended tobe limiting. Many variations and modifications of the disclosure arepossible and are within the scope of the invention. Use of the term“optionally” with respect to any element of a claim is intended to meanthat the subject element is required, or alternatively, is not required.Both alternatives are intended to be within the scope of the claim. Useof broader terms such as comprises, includes, having, etc. should beunderstood to provide support for narrower terms such as consisting of,consisting essentially of, comprised substantially of, etc.

Accordingly, the scope of protection is not limited by the descriptionset out above but is only limited by the claims which follow, that scopeincluding all equivalents of the subject matter of the claims. Each andevery claim is incorporated into the specification as an embodiment ofthe present invention. Thus, the claims are a further description andare an addition to the preferred embodiments of the present invention.The discussion of a reference in the Background is not an admission thatit is prior art to the present invention, especially any reference thatcan have a publication date after the priority date of this application.The disclosures of all patents, patent applications, and publicationscited herein are hereby incorporated by reference, to the extent thatthey provide exemplary, procedural or other details supplementary tothose set forth herein.

The following are enumerated embodiments, designated Group A, which areprovided as non-limiting examples:

Embodiment 1

An N²-phosphinyl formamidine compound having the formula:

wherein: R¹ is a C₁ to C₃₀ organyl group, R³ is hydrogen, a C₁ to C₃₀organyl group, or a C₁ to C₃₀ organyl group consisting essentially ofinert functional groups, and R⁴ and R⁵ are each independently a C₁ toC₃₀ organyl group consisting essentially of inert functional groups.

Embodiment 2

The N²-phosphinyl formamidine compound of embodiment 1, wherein R¹ is aC₁ to C₁₅ alkyl group, a C₄ to C₂₀ cycloalkyl group, a C₄ to C₂₀substituted cycloalkyl group, a C₆ to C₂₀ aryl group, or a C₆ to C₂₀substituted aryl group.

Embodiment 3

The N²-phosphinyl formamidine compound of embodiment 1, wherein R¹ is aphenyl group or a C₆ to C₂₀ substituted phenyl group.

Embodiment 4

The N²-phosphinyl formamidine compound of embodiment 1, wherein R¹ is aphenyl group, a 2-substituted phenyl group, a 4-substituted phenylgroup, a 2,4-disubstituted phenyl group, a 2,6-disubstituted phenylgroup, a 3,5-disubstituted phenyl group, or a 2,4,6-trisubstitutedphenyl group.

Embodiment 5

The N²-phosphinyl formamidine compound of embodiment 3 or 4, whereineach substituent of the substituted phenyl group is independently ahalide, a C₁ to C₅ alkyl group, or a C₁ to C₅ alkoxy group.

Embodiment 6

The N²-phosphinyl formamidine compound of embodiment 1, wherein R¹ is aphenyl group, a 2-methylphenyl group, a 2-ethylphenyl group, a2-isopropylphenyl group, a 2-tert-butylphenyl group, a 4-methylphenylgroup, a 4-ethylphenyl group, a 4-isopropylphenyl group, a4-tert-butylphenyl group, a 2,6-dimethylphenyl group, a2,6-diethylphenyl group, a 2,6-diisopropylphenyl group, a2-methyl-6-isopropylphenyl group, a 3,5-dimethylphenyl group, a2,4,6-trimethylphenyl group, or a 2,6-dimethyl-4-tert-butylphenyl group.

Embodiment 7

The N²-phosphinyl formamidine compound of any of embodiments 1 to 6,wherein R³ is hydrogen, a C₁ to C₁₀ alkyl group, a C₁ to C₁₅ cycloalkylgroup, a C₁ to C₁₅ substituted cycloalkyl group, a C₃ to C₁₅ aliphaticheterocyclic group, a C₃ to C₁₅ substituted aliphatic heterocyclicgroup, a C₆ to C₁₅ aryl group, a C₆ to C₁₅ substituted aryl group, a C₃to C₁₅ heteroaryl group, or a substituted C₃ to C₁₅ heteroaryl group.

Embodiment 8

The N²-phosphinyl formamidine compound of any of embodiments 1 to 6,wherein R³ is hydrogen.

Embodiment 9

The N²-phosphinyl formamidine compound of any of embodiments 1 to 8,wherein R⁴ and R⁵ are independently a C₁ to C₁₅ alkyl group, a C₄ to C₂₀cycloalkyl group, a C₄ to C₂₀ substituted cycloalkyl group, a C₃ to C₁₅aliphatic heterocyclic group, a C₃ to C₁₅ substituted aliphaticheterocyclic group, a C₆ to C₂₀ aryl group, a C₆ to C₂₀ substituted arylgroup, a C₃ to C₂₀ heteroaryl group, or a C₃ to C₂₀ substitutedheteroaryl group.

Embodiment 10

The N²-phosphinyl formamidine compound of any of embodiments 1 to 8,wherein R⁴ and R⁵ are independently a methyl group, an ethyl group, ann-propyl group, an n-butyl group, an n-pentyl group, or an n-hexylgroup.

Embodiment 11

The N²-phosphinyl formamidine compound of any of embodiments 1 to 8,wherein R⁴ and R⁵ are independently a methyl group, an ethyl group, anisopropyl group, a tert-butyl group, or a neopentyl group.

Embodiment 12

The N²-phosphinyl formamidine compound of any of embodiments 1 to 8,wherein R⁴ and R⁵ are each independently a cyclopentyl group, asubstituted cyclopentyl group, a cyclohexyl group, or a substitutedcyclohexyl group.

Embodiment 13

The N²-phosphinyl formamidine compound of any of embodiments 1 to 8,wherein R⁴ and R⁵ are independently a phenyl group or a C₆ to C₂₀substituted phenyl group.

Embodiment 14

The N²-phosphinyl formamidine compound of any of embodiments 1 to 8,wherein R⁴ and R⁵ are independently a phenyl group, a 2-substitutedphenyl group, a 4-substituted phenyl group, a 2,4-disubstituted phenylgroup, a 2,6-disubstituted phenyl group, a 3,5-disubstituted phenylgroup, or a 2,4,6-trisubstituted phenyl group.

Embodiment 15

The N²-phosphinyl formamidine compound of embodiment 1, wherein R¹ is aphenyl group or a C₆ to C₂₀ substituted phenyl group, R³ is hydrogen,and R⁴ and R⁵ are independently a C₁ to C₁₅ alkyl group, a C₄ to C₂₀cycloalkyl group, a C₄ to C₂₀ substituted cycloalkyl group, a C₆ to C₂₀aryl group, or a C₆ to C₂₀ substituted aryl group.

Embodiment 16

A method of preparing an N²-phosphinyl formamidine compound of any ofembodiments 1-21 comprising: a) contacting a metal alkyl with aformamidine to form a metal formamidinate; and b) contacting a phosphinehalide with the metal formamidinate to form a compound comprising anN²-phosphinyl formamidine group.

Embodiment 17

The method of embodiment 16, wherein the formamidine compound has theformula

and the phosphine halide has the formula

wherein X is chloride, bromide, or iodide.

Embodiment 18

The method of embodiment 16, wherein the formamidine compound isprepared by contacting an amine having the formula R¹NH₂ and atrihydrocarbylformate.

Embodiment 19

The method of embodiment 16, wherein the formamidine compound isprepared by contacting ammonium carbonate with a hydrocarboxymethaniminecompound having the formula

wherein R^(f) is a C₁ to C₁₀ hydrocarbyl group.

Embodiment 20

The method of embodiment 19, wherein the hydrocarboxymethaniminecompound is prepared by contacting trihydrocarbyl formate with aminehaving formula R¹NH₂.

Embodiment 21

A metal salt complex of the N²-phosphinyl formamidine compound of any ofembodiments 1 to 15, having the formula

or the formula

wherein MX_(p) represents the metal salt where M is a transition metal,X is a monoanion and p ranges from 2 to 6, or X is dianionic and pranges from 1 to 3, Q is a neutral ligand, and q ranges from 0 to 6.

Embodiment 22

The metal salt complex of embodiment 21, wherein the metal of the metalsalt is in a +2 or +3 oxidation state.

Embodiment 23

The metal salt complex of embodiment 21 or 22, wherein the metal saltcomprises chromium.

Embodiment 24

The metal salt complex of embodiment 21, wherein the metal salt is achromium(III) chloride.

Embodiment 25

A method of preparing the N²-phosphinyl formamidine metal salt complexof any of embodiments 21 to 24 having the formula

comprising: a) contacting a transition metal salt with an N²-phosphinylformamidine compound according to claim 1; and b) forming theN²-phosphinyl formamidine metal salt complex.

Embodiment 26

The method of embodiment 25, wherein the transition metal salt and theN²-phosphinyl formamidine compound are contacted at a transition metalsalt to N²-phosphinyl formamidine compound equivalent ratio of at least0.9:1.

Embodiment 27

The method of embodiment 25 or 26, wherein the transition metal salt andthe N²-phosphinyl formamidine compound are contacted in a solvent.

Embodiment 28

A catalyst system comprising a) the N²-phosphinyl formamidine metal saltcomplex of any of embodiments 21 to 24 and b) a metal alkyl.

Embodiment 29

The catalyst system of embodiment 28, wherein the metal alkyl comprisesan aluminoxane.

Embodiment 30

The catalyst system of embodiment 29, wherein the aluminoxane comprisesmethylaluminoxane (MAO), modified methylaluminoxane (MMAO),ethylaluminoxane, n-propylaluminoxane, iso-propylaluminoxane,n-butylaluminoxane, sec-butylaluminoxane, iso-butylaluminoxane, t-butylaluminoxane, 1-pentylaluminoxane, 2-pentylaluminoxane,3-pentylaluminoxane, iso-pentylaluminoxane, neopentylaluminoxane, ormixtures thereof.

Embodiment 31

The catalyst system of embodiment 29, wherein the aluminoxane comprisesmodified methylaluminoxane (MMAO).

Embodiment 32

The catalyst system of any of embodiments 29 to 31, wherein a molarratio of the aluminum of the aluminoxane to the metal of the metalcomplex is at least 5:1.

Embodiment 33

A method of preparing a catalyst system according to any of embodiments28 to 32, comprising forming a catalyst system mixture comprising a) theN²-phosphinyl formamidine metal salt complex of any of embodiments 21 to24 and b) the metal alkyl.

Embodiment 34

A process comprising: a) contacting an olefin and the catalyst system ofany of embodiments 28 to 32, wherein the metal alkyl is an aluminoxane;and b) forming an oligomer product.

Embodiment 35

A process comprising: a) forming a catalyst system mixture according toembodiment 33, wherein the metal alkyl is an aluminoxane; b) contactingthe catalyst system mixture with an olefin; and c) forming an oligomerproduct.

Embodiment 36

The process of embodiment 34 or 35, wherein the catalyst system orcatalyst system mixture further comprises a solvent.

Embodiment 37

The process of embodiment 34 or 35, wherein the catalyst system or thecatalyst system mixture is aged in the substantial absence of the olefinto form an aged catalyst system.

Embodiment 38

The process of embodiment 37, wherein the catalyst system or thecatalyst system mixture is aged at a temperature from 10° C. to 130° C.

Embodiment 39

The process of embodiment 37 or 38, wherein the catalyst system mixtureis aged for at least 20 minutes

Embodiment 40

The process of any of embodiments 34 to 39, wherein the oligomer productis formed at reaction conditions capable of forming an oligomer productcomprising a temperature ranging from 20° C. to 150° C.

Embodiment 41

The process of any of embodiments 34 to 40, wherein the olefin comprisesethylene.

Embodiment 42

The process of embodiment 41, wherein the ethylene partial pressure atwhich the oligomer product is formed is at least 50 psig.

Embodiment 44

The process of embodiment 41 or 42, wherein the olefin consistsessentially of ethylene and a liquid oligomer product comprising atleast 70 wt. % C₆ and C₈ olefins.

Embodiment 45

The process of embodiments 44, wherein the C₆ product in the oligomerproduct comprises at least 90 wt. % 1-hexene.

Embodiment 46

The process of embodiment 44 or 45, wherein the C₈ product in theoligomer product comprises at least 90 wt. % 1-octene.

Embodiment 47

The process of any of embodiments 34 to 46, wherein the catalyst systemor catalyst system mixture is contacted with the olefin and hydrogen andthe hydrogen partial pressure is at least 5 psig.

Embodiment 48

The process of any of embodiments 34 to 47, wherein R¹ is a phenyl groupor a C₆ to C₂₀ substituted phenyl group, R³ is hydrogen, R⁴ and R⁵ areindependently a C₁ to C₁₅ alkyl group, a C₄ to C₂₀ cycloalkyl group, aC₄ to C₂₀ substituted cycloalkyl group, a C₆ to C₂₀ aryl group, or a C₆to C₂₀ substituted aryl group, MX_(p) comprises a chromium (III) halide,Q is a THF, and q ranges from 0 to 6.

The following are enumerated embodiments, designated Group B, which areprovided as non-limiting examples:

A first embodiment which is an N²-phosphinyl formamidine compound havingthe formula:

-   -   wherein:    -   R¹ is a C₁ to C₃₀ organyl group,    -   R³ is hydrogen, a C₁ to C₃₀ organyl group, or a C₁ to C₃₀        organyl group consisting essentially of inert functional groups,        and    -   R⁴ and R⁵ are each independently a C₁ to C₃₀ organyl group        consisting essentially of inert functional groups.

A second embodiment which is a method of preparing an N²-phosphinylformamidine compound according to the first embodiment, comprising:

-   -   a) contacting a metal alkyl with a formamidine compound to form        a metal formamidinate; and    -   b) contacting a phosphine halide with the metal formamidinate to        form a compound comprising an N²-phosphinyl formamidine group.

A third embodiment which is a metal salt complex of an N²-phosphinylformamidine compound according to the first embodiment, having theformula

-   -   or the formula

-   -   wherein:    -   R¹ is a C₁ to C₃₀ organyl group,    -   R³ is hydrogen, a C₁ to C₃₀ organyl group, or a C₁ to C₃₀        organyl group consisting essentially of inert functional groups,    -   R⁴ and R⁵ are each independently a C₁ to C₃₀ organyl group        consisting essentially of inert functional groups,    -   MX_(p) represents the metal salt where M is a transition metal,        X is a monoanion and p ranges from 2 to 6, or X is a dianion and        p ranges from 1 to 3,    -   Q is a neutral ligand, and    -   q ranges from 0 to 6.

A fourth embodiment which is a method of preparing an N²-phosphinylformamidine metal salt complex according to the third embodiment havingthe formula

-   -   comprising:    -   a) contacting a transition metal salt with an N²-phosphinyl        formamidine compound according to embodiment 1; and    -   b) forming the N²-phosphinyl formamidine metal salt complex.

A fifth embodiment which is a catalyst system comprising a) anN²-phosphinyl formamidine metal salt complex according to the thirdembodiment and b) a metal alkyl.

A sixth embodiment which is a method of preparing a catalyst systemaccording to the fifth embodiment, comprising forming a catalyst systemmixture comprising a) the N²-phosphinyl formamidine metal salt complexaccording to embodiment 3 and b) the metal alkyl.

A seventh embodiment which is a process comprising:

-   -   a) contacting an olefin and the catalyst system according to        embodiment 5, wherein the metal alkyl is an aluminoxane; and    -   b) forming an oligomer product.

An eighth embodiment which is a process comprising:

-   -   a) forming a catalyst system mixture according to the sixth        embodiment, wherein the metal alkyl is an aluminoxane;    -   b) contacting the catalyst system mixture with an olefin; and    -   c) forming an oligomer product.

A ninth embodiment which is subject matter of any of the first throughthe eighth embodiments, wherein R¹ is a C₁ to C₁₅ alkyl group, a C₄ toC₂₀ cycloalkyl group, a C₄ to C₂₀ substituted cycloalkyl group, a C₆ toC₂₀ aryl group, or a C₆ to C₂₀ substituted aryl group.

A tenth embodiment which is the subject matter of any of the firstthrough the eighth embodiments, wherein R¹ is a phenyl group or a C₆ toC₂₀ substituted phenyl group.

An eleventh embodiment which is the subject matter of any of the firstthrough the eighth embodiments, wherein R¹ is a phenyl group, a2-substituted phenyl group, a 4-substituted phenyl group, a2,4-disubstituted phenyl group, a 2,6-disubstituted phenyl group, a3,5-disubstituted phenyl group, or a 2,4,6-trisubstituted phenyl group.

A twelfth embodiment which is the subject matter of any of the tenth orthe eleventh embodiment, wherein each substituent of the substitutedphenyl group is independently a halide, a C₁ to C₅ alkyl group, or a C₁to C₅ alkoxy group.

A thirteenth embodiment which is the subject matter of any of the firstthrough the eighth embodiments, wherein R¹ is a phenyl group, a2-methylphenyl group, a 2-ethylphenyl group, a 2-isopropylphenyl group,a 2-tert-butylphenyl group, a 4-methylphenyl group, a 4-ethylphenylgroup, a 4-isopropylphenyl group, a 4-tert-butylphenyl group, a2,6-dimethylphenyl group, a 2,6-diethylphenyl group, a2,6-diisopropylphenyl group, a 2-methyl-6-isopropylphenyl group, a3,5-dimethylphenyl group, a 2,4,6-trimethylphenyl group, or a2,6-dimethyl-4-tert-butylphenyl group.

A fourteenth embodiment which is the subject matter of any precedingembodiments, wherein R³ is hydrogen, a C₁ to C₁₀ alkyl group, a C₁ toC₁₅ cycloalkyl group, a C₁ to C₁₅ substituted cycloalkyl group, a C₃ toC₁₅ aliphatic heterocyclic group, a C₃ to C₁₅ substituted aliphaticheterocyclic group, a C₆ to C₁₅ aryl group, a C₆ to C₁₅ substituted arylgroup, a C₃ to C₁₅ heteroaryl group, or a substituted C₃ to C₁₅heteroaryl group.

A fifteenth embodiment which is the subject matter of any precedingembodiments, wherein R³ is hydrogen.

A sixteenth embodiment which is the subject matter of any precedingembodiments, wherein R⁴ and R⁵ are independently a C₁ to C₁₅ alkylgroup, a C₄ to C₂₀ cycloalkyl group, a C₄ to C₂₀ substituted cycloalkylgroup, a C₃ to C₁₅ aliphatic heterocyclic group, a C₃ to C₁₅ substitutedaliphatic heterocyclic group, a C₆ to C₂₀ aryl group, a C₆ to C₂₀substituted aryl group, a C₃ to C₂₀ heteroaryl group, or a C₃ to C₂₀substituted heteroaryl group.

A seventeenth embodiment which is the subject matter of any precedingembodiments, wherein R⁴ and R⁵ are independently a methyl group, anethyl group, an isopropyl group, a tert-butyl group, or a neopentylgroup.

An eighteenth embodiment which is the subject matter of any precedingembodiments, wherein R⁴ and R⁵ are independently a methyl group, anethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, oran n-hexyl group.

A nineteenth embodiment which is the subject matter of any of the firstthrough the sixteenth embodiments, wherein R⁴ and R⁵ are eachindependently a cyclopentyl group, a substituted cyclopentyl group, acyclohexyl group, or a substituted cyclohexyl group.

A twentieth embodiment which is the subject matter of any of the firstthrough the sixteenth embodiments, wherein R⁴ and R⁵ are independently aphenyl group or a C₆ to C₂₀ substituted phenyl group.

A twenty-first embodiment which is the subject matter of any of thefirst through the sixteenth embodiments, wherein R⁴ and R⁵ areindependently a phenyl group, a 2-substituted phenyl group, a4-substituted phenyl group, a 2,4-disubstituted phenyl group, a2,6-disubstituted phenyl group, a 3,5-disubstituted phenyl group, or a2,4,6-trisubstituted phenyl group.

A twenty-second embodiment which is the subject matter of any of thefirst through the eighth embodiments, wherein

-   -   R¹ is a phenyl group or a C₆ to C₂₀ substituted phenyl group,    -   R³ is hydrogen, and    -   R⁴ and R⁵ are independently a C₁ to C₁₅ alkyl group, a C₄ to C₂₀        cycloalkyl group, a C₄ to C₂₀ substituted cycloalkyl group, a C₆        to C₂₀ aryl group, or a C₆ to C₂₀ substituted aryl group.

A twenty-third embodiment which is the method of the second embodiment,wherein the formamidine compound is prepared by contacting an aminehaving the formula R¹NH₂ and a trihydrocarbylformate.

A twenty-fourth embodiment which is the method of the second embodiment,wherein the formamidine compound is prepared by contacting ammoniumcarbonate with a hydrocarboxymethanimine compound having the formula

wherein R¹ is a C₁ to C₃₀ organyl group and R⁶ is a C₁ to C₁₀hydrocarbyl group.

A twenty-fifth embodiment which is the method of the twenty-fourthembodiment, wherein the hydrocarboxymethanimine compound is prepared bycontacting trihydrocarbyl formate with amine having formula R¹NH₂wherein R¹ is a C₁ to C₃₀ organyl group.

A twenty-sixth embodiment which is the subject matter of any of thethird through the eighth embodiments, wherein the metal of the metalsalt is in a +2 or +3 oxidation state.

A twenty-seventh embodiment which is the subject matter of any of thethird through the eighth embodiments, wherein the metal salt compriseschromium.

A twenty-eighth embodiment which is the subject matter of any of thethird through the eighth embodiments, wherein the metal salt is achromium(III) chloride.

A twenty-ninth embodiment which is the method of the fourth embodiment,wherein the transition metal salt and the N²-phosphinyl formamidinecompound are contacted at a transition metal salt to N²-phosphinylformamidine compound equivalent ratio of at least 0.9:1.

A thirtieth embodiment which is the method of the fourth embodiment,wherein the transition metal salt and the N²-phosphinyl formamidinecompound are contacted in a solvent.

A thirty-first embodiment which is the subject matter of any of thefifth through the eighth embodiments, wherein the metal alkyl comprisesan aluminoxane and the aluminoxane comprises methylaluminoxane (MAO),modified methylaluminoxane (MMAO), ethylaluminoxane,n-propylaluminoxane, iso-propylaluminoxane, n-butylaluminoxane,sec-butylaluminoxane, iso-butylaluminoxane, t-butyl aluminoxane,1-pentylaluminoxane, 2-pentylaluminoxane, 3-pentylaluminoxane,iso-pentylaluminoxane, neopentylaluminoxane, or mixtures thereof.

A thirty-second embodiment which is the subject matter of thethirty-first embodiment, wherein the aluminoxane comprises modifiedmethylaluminoxane (MMAO).

A thirty-third embodiment which is the subject matter of thethirty-first embodiment, wherein a molar ratio of the aluminum of thealuminoxane to the metal of the metal complex is at least 5:1.

A thirty-fourth embodiment which is the subject matter of any of thesixth or the eighth embodiment, wherein the catalyst system or catalystsystem mixture further comprises a solvent.

A thirty-fifth embodiment which is the process of any of the seventh orthe eighth embodiment, wherein the catalyst system or the catalystsystem mixture is aged in the substantial absence of the olefin to forman aged catalyst system.

A thirty-sixth embodiment which is the process of the thirty-fifthembodiment, wherein the catalyst system or the catalyst system mixtureis aged at a temperature from 10° C. to 130° C.

A thirty-seventh embodiment which is the process of any of thethirty-fifth or the thirty-sixth embodiment, wherein the catalyst systemmixture is aged for at least 20 minutes

A thirty-eighth embodiment which is the process of any of the seventh,the eighth or the thirty-fifth through thirty-seventh embodiments,wherein the oligomer product is formed at reaction conditions capable offorming an oligomer product comprising a temperature ranging from 20° C.to 150° C.

A thirty-ninth embodiment which is the process of any of the seventh,the eighth or the thirty-fifth through thirty-seventh embodiments,wherein the olefin comprises ethylene.

A fourteenth embodiment which is the process of the thirty-ninthembodiment, wherein the ethylene partial pressure at which the oligomerproduct is formed is at least 50 psig.

A forty-first embodiment which is the process of any of the seventh, theeighth or the thirty-fifth through thirty-seventh embodiments, whereinthe olefin consists essentially of ethylene and a liquid oligomerproduct comprising at least 70 wt. % C₆ and C₈ olefins.

A forty-second embodiment which is the process of the forty-firstembodiment, wherein the C₆ product in the oligomer product comprises atleast 90 wt. % 1-hexene.

A forty-third embodiment which is the process of the forty-firstembodiment, wherein the C₈ product in the oligomer product comprises atleast 90 wt. % 1-octene.

A forty-fourth embodiment which is the process of the eighth embodiment,wherein the catalyst system mixture is contacted with the olefin andhydrogen and the hydrogen partial pressure is at least 5 psig.

A forty-fifth embodiment which is the process of any of the seventh, theeighth or the thirty-fifth through forty-second embodiments, wherein

-   -   R¹ is a phenyl group or a C₆ to C₂₀ substituted phenyl group,    -   R³ is hydrogen,    -   R⁴ and R⁵ are independently a C₁ to C₁₅ alkyl group, a C₄ to C₂₀        cycloalkyl group, a C₄ to C₂₀ substituted cycloalkyl group, a C₆        to C₂₀ aryl group, or a C₆ to C₂₀ substituted aryl group,    -   MX_(p) comprises a chromium (III) halide,    -   Q is a THF, and    -   q ranges from 0 to 6.

What is claimed:
 1. A catalyst system comprising a) an N²-phosphinylformamidine metal salt complex having the formula

or the formula

wherein: R¹ is a C₁ to C₃₀ organyl group, R³ is hydrogen, R⁴ and R⁵ areeach independently a C₁ to C₃₀ organyl group consisting essentially ofinert functional groups, wherein each inert functional groupindependently is a halo group, a nitro group, a hydrocarboxy group, asulfidyl group, or a hydrocarbyl group, MX_(p) represents the metal saltwhere M is a Group 6 transition metal, X is a monoanion and p rangesfrom 2 to 6, or X is a dianion and p ranges from 1 to 3, O is a neutralligand, and q ranges from 0 to 6, and b) a metal alkyl.
 2. The catalystsystem of claim 1, wherein R¹ is a C₁ to C₁₅ alkyl group, a C₄ to C₂₀cycloalkyl group, a C₄ to C₂₀ substituted cycloalkyl group, a C₆ to C₂₀aryl group, or a C₆ to C₂₀ substituted aryl group, and R⁴ and R⁵ areindependently a C₁ to C₁₅ alkyl group, a C₄ to C₂₀ cycloalkyl group, aC₄ to C₂₀ substituted cycloalkyl group, a C₃ to C₁₅ aliphaticheterocyclic group, a C₃ to C₁₅ substituted aliphatic heterocyclicgroup, a C₆ to C₂₀ aryl group, a C₆ to C₂₀ substituted aryl group, a C₃to C₂₀ heteroaryl group, or a C₃ to C₂₀ substituted heteroaryl group. 3.The catalyst system of claim 1, wherein R¹ is a phenyl group or a C₆ toC₂₀ substituted phenyl group, R⁴ and R⁵ are independently a C₁ to C₁₅alkyl group, a C₄ to C₂₀ cycloalkyl group, a C₄ to C₂₀ substitutedcycloalkyl group, a C₆ to C₂₀ aryl group, or a C₆ to C₂₀ substitutedaryl group, M is chromium, X is a halide, a C₁ to C₂₀ carboxylate, a C₁to C₂₀ β-diketonate, or a C₁ to C₂₀ hydrocarboxide, p is ranges from 2to 3, and Q is a C₂ to C₂₀ nitrile or a C₂ to C₄₀ either.
 4. Thecatalyst system of claim 3, wherein the metal alkyl comprises analuminoxane and the aluminoxane comprises methylaluminoxane (MAO),modified methylaluminoxane (MMAO), ethylaluminoxane,n-propylaluminoxane, iso-propylaluminoxane, n-butylaluminoxane,sec-butylaluminoxane, iso-butylaluminoxane, t-butyl aluminoxane,1-pentylaluminoxane, 2-pentylaluminoxane, 3-pentylaluminoxane,iso-pentylaluminoxane, neopentylaluminoxane, or mixtures thereof.
 5. Thecatalyst system of claim 4, wherein a molar ratio of the aluminum of thealuminoxane to the metal of the metal complex is at least 5:1.
 6. Amethod of preparing a catalyst system of claim 1, comprising forming acatalyst system mixture comprising a) the N²-phosphinyl formamidinemetal salt complex and h) the metal alkyl.
 7. The method of claim 6,wherein the catalyst system or the catalyst system mixture is aged forat least 20 minutes in the substantial absence of the olefin to form anaged catalyst system.
 8. A process comprising: a) forming a catalystsystem mixture according to claim 6, wherein the metal alkyl is analuminoxane; b) contacting the catalyst system mixture with an olefin;and c) forming an oligomer product.
 9. The process of claim 8, whereinthe catalyst system or the catalyst system mixture is aged for at least20 minutes in the substantial absence of the olefin to form an agedcatalyst system.
 10. A process comprising: a) contacting an olefin andthe catalyst system of claim 1, wherein the metal alkyl is analuminoxane; and b) forming an oligomer product.
 11. The process ofclaim 10, wherein R¹ is a C₁ to C₁₅ alkyl group, a C₄ to C₂₀ cycloalkylgroup, a C₄ to C₂₀ substituted cycloalkyl group, a C₆ to C₂₀ aryl group,or a C₆ to C₂₀ substituted aryl group, and R⁴ and R⁵ are independently aC₁ to C₁₅ alkyl group, a C₄ to C₂₀ cycloalkyl group, a C₄ to C₂₀substituted cycloalkyl group, a C₃ to C₁₅ aliphatic heterocyclic group,a C₃ to C₁₅ substituted aliphatic heterocyclic group, a C₆ to C₂₀ arylgroup, a C₆ to C₂₀ substituted aryl group, a C₃ to C₂₀ heteroaryl group,or a C₃ to C₂₀ substituted heteroaryl group.
 12. The process of claim10, wherein R¹ is a phenyl group or a C₆ to C₂₀ substituted phenylgroup, R⁴ and R⁵ are independently a C₁ to C₁₅ alkyl group, a C₄ to C₂₀cycloalkyl group, a C₄ to C₂₀ substituted cycloalkyl group, a C₆ to C₂₀aryl group, or a C₆ to C₂₀ substituted aryl group, M is chromium, X is ahalide, a C₁ to C₂₀ carboxylate, a C₁ to C₂₀ β-diketonate, or a C₁ toC₂₀ hydrocarboxide, p is ranges from 2 to 3, and Q is a C₂ to C₂₀nitrite or a C₂ to C₄₀ ether.
 13. The process of claim 12, wherein thealuminoxane comprises methylaluminoxane (MAO), modifiedmethylaluminoxane (MMAO), ethylaluminoxane, n-propylaluminoxane,iso-propylaluminoxane, n-butylaluminoxane, sec-butylaluminoxane,iso-butyl aluminoxane, t-butyl aluminoxane, 1-pentylaluminoxane,2-pentylaluminoxane, 3-pentylaluminoxane, iso-pentylaluminoxane,neopentylaluminoxane, or mixtures thereof.
 14. The process of claim 13,wherein the olefin comprises ethylene and the ethylene partial pressureranges from 50 psig to 4,000 psig.
 15. The process of claim 14, whereinthe a molar ratio of the aluminum of the aluminoxane to the metal of themetal salt complex is at least 5:1, the oligomer product is formed at atemperature ranging from 20° C. to 150° C., and optionally whereinhydrogen is contacted with the catalyst system mixture and the olefinand the hydrogen partial pressure ranges from 5 psig to 400 psig. 16.The process of claim 15, wherein a liquid oligomer product comprises atleast 70 wt. % C₆ and C₈ olefins.